Laminate and optical article comprising the same

ABSTRACT

To provide a laminate comprising a pair of polycarbonate optical sheet or film which are laminated together through a polarizing film layer and an adhesive layer of a photochromic composition comprising (I) a polyurethane urea resin and (II) a photochromic compound and having excellent photochromic properties, adhesion, heat resistance, perspiration resistance and excellent adhesion to a lens substrate.

TECHNICAL FIELD

The present invention relates to a laminate which is used to producelenses such as polarizing lenses having polarization properties andsunglass lenses having photochromic properties and an optical articlecomprising the laminate.

BACKGROUND ART

Demand for plastic substrates composed of polycarbonate havingtransparency and excellent impact resistance for use in sunglasseshaving glare shielding property is now growing rapidly mainly in theU.S. Plastic photochromic sunglasses which are capable of controllingglare shielding property due to variations in transmittance according tosurrounding brightness and the amount of ultraviolet light by combiningphotochromic properties are becoming popular rapidly. These sunglassesare now manufactured by the following method.

For example, as means for forming a functional layer having glareshielding property between two plastic sheets or films, there is known amethod in which a photochromic layer is formed between two polycarbonatesheets (refer to Japan Patent No. 4661017). Stated more specifically, aphotochromic coating solution containing a solvent is applied to one ofthe plastic sheets, let pass through a drier having a specifictemperature at a specific rate to be dried, and bonded to the otherplastic sheet to produce a laminate. According to this method, alaminate having an adhesive layer with excellent smoothness can beproduced continuously.

Further, the above laminate having a photochromic layer can be formedinto a desired shape by carrying out thermal bending in which thelaminate is shaped under an increased or reduced pressure (vacuum) in aheating environment, for example, at a heating temperature close to theglass transition temperature of the laminate by using a mold which hasbeen caved into a desired shape in advance. The laminate is generallydiecut into a desired shape before or after the above thermal bending.

Further, the laminate which has been thermally bent is set in the moldof an injection molding machine, and a thermoplastic resin is injectionmolded on the concave side of the thermally bent laminate to integratean optical substrate composed of the thermoplastic resin with thelaminate, thereby producing sunglasses.

Sunglasses provided with both polarization properties and photochromicproperties were developed in order to adjust transmittance according tosurrounding brightness and the amount of ultraviolet light whilesuppressing the glare of reflected light.

As means for manufacturing the sunglasses provided with bothpolarization properties and photochromic properties, there is known amethod in which a photochromic layer and a polarizing layer are formedbetween two polycarbonate films (refer to Japan Patent No. 4586953).Stated more specifically, after a photochromic coating solutioncontaining a solvent is applied to a polarizing film, dried and bondedto a polycarbonate film, a urethane-based adhesive is applied to theother side of the polarizing film, dried and bonded to the otherpolycarbonate sheet so as to produce a laminate. According to thismethod, a laminate having an adhesive layer with excellent smoothnesscan be produced continuously.

There is also known a method in which a photochromic layer and apolarizing layer are formed between a cellulose triacetate film and apolycarbonate film (refer to Japan Patent No. 5037614). Stated morespecifically, Japan Patent No. 5037614 discloses the following method. Apolarizing sheet having a polarizing layer between two cellulosetriacetate films is prepared, and a two-liquid curable urethane resin isapplied as an adhesive to one side of the polarizing sheet to bond apolycarbonate film thereto. Then, a two-liquid curable urethane resincontaining a photochromic compound is applied as an adhesive to theother side of the polarizing sheet to bond a cellulose triacetate filmthereto, thereby producing a laminate. According to this method, alaminate having an adhesive layer with excellent smoothness andphotochromic properties can be produced continuously.

However, according to studies conducted by the inventors of the presentinvention, it was found that the adhesion (adhesion between plasticsheets) of each of the laminates produced by the methods disclosed byJapan Patent No. 4661017, Japan Patent No. 4586953 and Japan Patent No.5037614 is inferior in terms of “perspiration resistance” which isrequired for sunglasses, that is, a state that a laminate does notchange even when in contact with human perspiration. That is, it wasfound that in sunglasses which comprise a conventional laminate, theinterface between the adhesive layer and the polycarbonate sheet orbetween the adhesive layer and the cellulose triacetate film mayseparate.

As means for improving adhesion between the photochromic layer and theoptical sheet or optical film, there is proposed a method in which aphotochromic polyurethane urea resin layer formed by using aphotochromic compound and a polyurethane urea resin and an optical sheetor optical film are laminated through an adhesive layer (refer to JP-A2013-33131).

DISCLOSURE OF THE INVENTION

A laminate having excellent adhesion and including a photochromic layerand a polarizing layer can be obtained by the method of JP-A 2013-33131.

However, the laminate obtained by this method is constituted such thatthe front surface and rear surface of the laminate are composed ofsheets composed of different materials, that is, a cellulose triacetatefilm and a polycarbonate sheet. To fully develop photochromic propertiesas sunglasses, a photochromic layer must be situated on the side to beirradiated with sunlight with respect to a polarizing sheet. Therefore,the optimal lamination order of the laminate from the side to beirradiated with sunlight is a polycarbonate sheet, a photochromic layer,a cellulose triacetate film, a polarizing layer and a cellulosetriacetate film.

However, according to studies conducted by the inventors of the presentinvention, it was found that when a thermoplastic resin such aspolycarbonate resin is injection molded on the rear surface layeropposite to the side to be irradiated with sunlight, that is, thecellulose triacetate film layer to manufacture a lens integrated withthe above laminate, adhesion between the cellulose triacetate film andthe thermoplastic resin in the laminate having the above laminationorder becomes unsatisfactory.

It is therefore an object of the present invention to provide a laminatehaving excellent photochromic properties, adhesion, heat resistance andperspiration resistance and further a laminate having excellent adhesionbetween the above laminate and a lens substrate.

The inventors of the present invention conducted intensive studies tosolve the above problem and found that the following conditions arerequired when a polycarbonate layer as a thermoplastic resin layer isinjection molded on the rear side of a laminate to manufacture a lensintegrated with the laminate. That is, they found that adhesion betweena laminate and a lens substrate can be improved by using an opticalsheet or film composed of polycarbonate which is the same thermoplasticresin as a polycarbonate layer to be injected as the rear surface of thelaminate and a specific resin in a photochromic layer. The presentinvention was thus accomplished based on this finding.

That is, the present invention is (1) a laminate comprising a pair ofpolycarbonate optical sheets or films which are laminated togetherthrough a polarizing film layer and an adhesive layer of a photochromiccomposition comprising (I) a polyurethane urea resin and (II) aphotochromic compound.

The above laminate of the present invention can take the followingmodes.

(2) The polydispersity, that is, weight average molecular weight/numberaverage molecular weight ratio of the above polyurethane urea resin (I)is 1.6 to 2.4.

(3) The above photochromic composition further comprises (III) apolyisocyanate compound having at least two isocyanate groups in themolecule.

(4) The polyisocyanate compound having at least two isocyanate groups inthe molecule (III) is at least one polyisocyanate compound selected fromthe group consisting of a compound having an isocyanate group bonded toa secondary carbon, hexamethylene diisocyanate, burette compound ofhexamethylene diisocyanate, isocyanurate compound of hexamethylenediisocyanate and adduct compound of hexamethylene diisocyanate.

(5) The above polyisocyanate compound having at least two isocyaninegroups in the molecule (III) comprises (IIIA) a compound having anisocyanate group bonded to a secondary carbon and (IIIB) at least onecompound selected from the group consisting of hexamethylenediisocyanate, burette compound of hexamethylene diisocyanate,isocyanurate compound of hexamethylene diisocyanate and adduct compoundof hexamethylene diisocyanate.

(6) The above polyisocyanate compound having at least two isocyanategroups in the molecule (III) comprises 100 parts by mass of the compoundhaving an isocyanate group bonded to a secondary carbon (IIIA) and 20 to150 parts by mass of at least one compound (IIIB) selected from thegroup consisting of hexamethylene diisocyanate, burette compound ofhexamethylene diisocyanate, isocyanurate compound of hexamethylenediisocyanate and adduct compound of hexamethylene diisocyanate.

(7) The above polyurethane urea resin (I) is a reaction product of (A) aurethane prepolymer having an isocyanate group at the end of themolecule, (B) a polyamine compound having at least two amino groups inthe molecule and (C) a compound having one group able to react with anisocyanate group in the molecule.

(8) The above polycarbonate optical sheets or films and the polarizingfilm layer and/or the polarizing film layer and the adhesive layer ofthe photochromic composition are laminated together through an adhesivelayer containing no photochromic compound.

(9) At least one optical sheet or film is existent between the abovepolarizing film layer and the above adhesive layer of the photochromiccomposition.

(10) A cellulose triacetate film is laminated on both sides of thepolarizing film layer.

(11) The softening point of the above adhesive layer of the photochromiccomposition is not lower than 100° C.

(12) The softening points of the above adhesive layer of thephotochromic composition and the above adhesive layer containing nophotochromic compound are not lower than 100° C.

(13) The polycarbonate optical sheet or film, the above adhesive layercontaining no photochromic compound, the above adhesive layer of thephotochromic composition, the polarizing film layer, the above adhesivelayer containing no photochromic compound and the polycarbonate opticalsheet or film are laminated in this order.

(14) The adhesive layer of the photochromic composition described beforethe polarizing film differs from the adhesive layer containing nophotochromic compound described after the polarizing film only in thatthe former layer contains the photochromic compound.

(15) An adhesive layer which differs from the adhesive layer containingno photochromic compound is further existent between the adhesive layercontaining no photochromic compound described after the polarizing filmlayer and the polycarbonate optical sheet or film.

(16) Further, in another invention of the present invention, an opticalarticle having a polycarbonate layer on the front surface of apolycarbonate optical sheet or film on the polarizing film layer side ofthe laminate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a drawing for explaining a first example showing theconstitution of the laminate of the present invention.

FIG. 2 is a drawing for explaining the constitution of an opticalarticle formed by using the laminate of the present invention.

FIG. 3 is a drawing for explaining a second example showing theconstitution of the laminate of the present invention.

FIG. 4 is a drawing for explaining a third example showing theconstitution of the laminate of the present invention.

FIG. 5 is a drawing for explaining a fourth example showing theconstitution of the laminate of the present invention.

PRACTICAL EMBODIMENT OF THE INVENTION

The laminate of the present invention is a laminate formed by laminatinga pair of polycarbonate optical sheets or films through a polarizingfilm layer and an adhesive layer composed of a photochromic compositioncomprising (I) a polyurethane urea resin and (II) a photochromiccompound. With reference to FIG. 1, the present invention will bedescribed by taking the laminate of the present invention as an example.

Referring to FIG. 1, the laminate 4 of the present invention isconstituted such that a pair of opposed polycarbonate optical sheets orfilms 1 and 1′ contain a polarizing film layer 3 and an adhesive layer 2composed of a photochromic composition. In the following description,the exposed surface of an optical sheet or film on the adhesive layerside composed of the photochromic composition of the laminate will bereferred to as “front surface” and the exposed surface of an opticalsheet or film on the polarizing film side will be referred to as “rearsurface”. As will be described in detail hereinunder, the polycarbonateoptical sheet or film 1 existent on the front side of the laminate inFIGS. 1 to 5 is preferably stretched in a monoaxial direction which isthe same axial direction as the polarizing film which will be describedhereinafter.

FIG. 2 shows an example of an optical article formed by using thelaminate of the present invention. That is, this is an optical article 6which includes a polycarbonate optical sheet or film 1′ used as the rearsurface of the laminate 4 of the present invention and a lens substrate5 which is obtained by injection molding a polycarbonate which is athermoplastic resin to form a polycarbonate layer on the rear side.

FIG. 3 shows a second example showing the constitution of the laminateof the present invention. This is constituted such that a pair ofopposed polycarbonate optical sheets or films 1 and 1′ contain apolarizing film layer 3 and an adhesive layer 2 composed of aphotochromic composition. This is a laminate in which a third opticalsheet or film 7 or a polycarbonate optical sheet or film 1′ is attachedto both sides of the polarizing layer 3 through adhesive layers 8.

FIG. 4 shows a third example showing the constitution of the laminate ofthe present invention. This is constituted such that a pair of opposedpolycarbonate optical sheets or films 1 and 1′ contain a polarizing filmlayer 3 and an adhesive layer 2 composed of a photochromic composition.Third optical sheets or films 7 are adhering to both sides of thepolarizing film layer 3, respectively, one of the third optical sheetsor films 7 is formed on an adhesive layer 2 composed of a photochromiccomposition, and the other third optical sheet or film 7 is attached tothe polycarbonate optical sheet or film 1′ through an adhesive layer 8.

FIG. 5 shows a fourth example showing the constitution of the laminateof the present invention. This is constituted such that a pair ofopposed polycarbonate optical sheets or films 1 and 1′ contain apolarizing film layer 3 and an adhesive layer 2 composed of aphotochromic composition. The laminate includes, from the toppolycarbonate optical sheet or film 1, an adhesive layer 8, the adhesivelayer 2 composed of a photochromic composition, the polarizing filmlayer 3, an adhesive layer 9, an adhesive layer 8 and the polycarbonateoptical sheet or film 1′ in this order. Although the adhesive layer 9 isnot essential, when the adhesive layer 9 is existent, adhesion isfurther improved. Especially when an optical article 6 is obtained byforming a polycarbonate lens substrate 5 on the surface of thepolycarbonate optical sheet or film 1′ by injection molding, the effectof improving adhesion is obtained notably.

Although the adhesive layer 8 and the adhesive layer 9 do not contain aphotochromic compound in the above examples of the laminate, they differfrom each other in adhesive.

A detailed description is subsequently given of each constituentcomponent of the laminate of the present invention. A pair of opposedpolycarbonate optical sheets or films in the present invention will befirst explained.

<Polycarbonate Optical Sheets or Films>

In the present invention, as the polycarbonate optical sheets or films,dyed films or dyed sheets may be used. As a matter of course, films orsheets which are not dyed may also be used. When dyed polycarbonatesheets or films are used, films or sheets which have been dyed may beused or a polycarbonate sheet or film on the front side may be dyedafter the production of the laminate of the present invention.

It is preferred that the adhesive layer composed of a photochromiccomposition should be laminated such that it is irradiated with sunlightor ultraviolet light before the dyed films in the laminate including thedyed films or dyed sheets.

The thickness of each of the polycarbonate optical sheets or films usedin the present invention is preferably 30 to 1,000 μm, more preferably50 to 400 μm. The polycarbonate optical sheets or films may be acombination of sheets or films which differ in thickness.

As the polycarbonate optical sheets or films used in the presentinvention, from the viewpoint of optical distortion, optical sheets orfilms which have been stretched in a monoaxial direction which is thesame axial direction as that of the polarizing film which will bedescribed hereinafter are preferably used. Further, the optical films orsheets which have been stretched monoaxially preferably have a phasedifference of not less than 3,000 nm.

When the polycarbonate optical sheets or films which have been stretchedmonoaxially are used, at least one of them should be used as thepolycarbonate optical sheet or film existent on the front side of thelaminate. The other polycarbonate optical sheet or film (including thepolycarbonate optical sheet or film existent on the rear side of thelaminate) may be an optical sheet or film which has been stretchedmonoaxially or not stretched.

A description is subsequently given of the polarizing film layer used inthe present invention.

<Polarizing Film Layer>

As the polarizing film layer in the present invention, any knownpolarizing film may be used. Preferably, the polarizing film has athickness of 10 to 200 μm, a total light transmittance of not less than30% and a polarization degree of not less than 95.0%. More preferably,the polarizing film has a thickness of 10 to 100 μm, a total lighttransmittance of not less than 40%, and a polarization degree of notless than 99.0%. When the industrial-scale production of the polarizingfilm itself is taken into consideration, the upper limit of total lighttransmittance is 50% and the upper limit of polarization degree is 100%.

In the present invention, the above polarizing film layer is formed bydyeing a polyvinyl alcohol-based film which is generally used as a basefilm with iodine which is a dichromatic substance or a dichromatic dyeand stretching the dyed polyvinyl alcohol-based film monoaxially.

A description is subsequently given of the adhesive layer composed of aphotochromic composition used in the present invention. In the presentinvention, the adhesive layer composed of a photochromic compositioncomprises (I) a polyurethane urea resin and (II) a photochromiccompound. A description is first given of the polyurethane urea resin(I) contained in the photochromic composition.

<Photochromic Composition> <(I) Polyurethane Urea Resin>

In the present invention, the polyurethane urea resin (I) has a ureabond (—R—NH—CO—NH—) in the molecular chain. Any known polyurethane urearesin may be used. From the viewpoints of adhesion, heat resistance andperspiration resistance, it is preferably a reaction product of (A) aurethane prepolymer having an isocyanate group at the end of themolecule, (B) a polyamine compound having at least two amino groups inthe molecule and (C) a compound having one group able to react with anisocyanate group in the molecule. In this polyurethane urea resin, theurea bond is introduced into the molecule due to the use of thepolyamine compound as the component (B) which is a raw material. Adescription is subsequently given of these components. The polyurethaneurea resin (I) may be simply referred to as “component (I)” hereinafter.

<Component A: Urethane Prepolymer Having an Isocyanate Group at the Endof the Molecule>

A known urethane prepolymer may be used as the urethane prepolymerhaving an isocyanate group at the end of the molecule (component A)which is a constituent component of the above polyurethane urea resin.It is preferably a reaction product of (A1) at least one polyol compoundselected from the group consisting of polyols having at least twohydroxyl groups such as polyether polyols, polyester polyols,polycarbonate polyols and polycaprolactone polyols and (A2) adiisocyanate compound having two isocyanate groups in the molecule.

<Component A1: At Least One Polyol Compound Selected from the GroupConsisting of Polyols Having at Least Two Hydroxyl Groups Such asPolyether Polyols, Polyester Polyols, Polycarbonate Polyols SandPolycaprolactone Polyols>

The number of hydroxyl groups contained in one molecule of the abovepolyol compound (component A1) is preferably 2 to 6 for the reason thatthe formed polyurethane urea resin (component I) does not become ahighly crosslinked material. The number of hydroxyl groups contained inthe molecule is more preferably 2 to 3 in consideration of solubility inan organic solvent. The above polyol compounds such as polyetherpolyols, polyester polyols, polycarbonate polyols and polycaprolactonepolyols may be used alone or in combination of two or more. Out ofthese, polycarbonate polyols and polycaprolactone polyols are preferablyused from the viewpoints of heat resistance, adhesion, weatherabilityand hydrolysis resistance. A detailed description is given of eachcompound used as the component A1.

<Polycarbonate Polyol>

Examples of the polycarbonate polyol used as the component A1 includepolycarbonate polyols obtained by phosgenating at least onelow-molecular weight polyol such as ethylene glycol, 1,2-propanediol,1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethyleneglycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol,cyclohexane-1,4-dimethanol, dimeric acid diol, ethylene oxide orpropylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene,xylylene glycol, glycerin, trimethylolpropane or pentaerythritol or bytransesterifying a low-molecular weight carbonate such as ethylenecarbonate, diethyl carbonate or diphenyl carbonate. Out of theselow-molecular weight polyols, low-molecular weight polyols having alinear alkylene chain are more preferred from the viewpoints of theadhesion and heat resistance of the finally obtained polyurethane urearesin (component I). Polycarbonate polyols synthesized fromlow-molecular weight polyols having an alkyl group in the side chaintend to deteriorate in adhesion as compared with low-molecular weightpolyols having a linear alkylene chain.

The number average molecular weight of the polycarbonate polyol as thecomponent A1 is preferably 400 to 2,000, more preferably 500 to 1,500,most preferably 600 to 1,200 from the viewpoint of the heat resistanceof the finally obtained polyurethane urea resin (component I).

These polycarbonate polyols can be acquired industrially as a reagent.Commercially available products thereof include the Duranol (registeredtrademark) series of Asahi Kasei Chemicals Corporation, the KurarayPolyol (registered trademark) series of Kuraray Co., Ltd., the Placcel(registered trademark) series of Daicel Chemical Industries, Ltd., theNipporan (registered trademark) series of Nippon Polyurethane IndustryCo., Ltd., and the ETERNACOLL (registered trademark) series of UbeIndustries., Ltd.

<Polycaprolactone Polyol>

The polycaprolactone polyol used as the component A1 is preferably acompound obtained by the ring-opening polymerization of ε-caprolactone.The number average molecular weight of the polycaprolactone polyol asthe component A1 is preferably 400 to 2,000, more preferably 500 to1,500, most preferably 600 to 1,200 for the same reason as that of thepolycarbonate polyol.

The polycaprolactone polyol can be acquired industrially as a reagent.Commercially available products thereof include the Placcel (registeredtrademark) series of Daicel Chemical Industries, Ltd.

<Polyether Polyol>

Examples of the polyether polyol include polyether polyol compoundsobtained from a reaction between a compound having at least two activehydrogen-containing groups in the molecule and an alkylene oxide,polymer polyols which are modified products of the polyether polyolcompounds, urethane modified polyether polyols and polyether estercopolymer polyols.

Examples of the compound having at least two active hydrogen-containinggroups in the molecule include polyol compounds such as glycols andglycerin having at least one hydroxyl group in the molecule exemplifiedby water, ethylene glycol, propylene glycol, butanediol, glycerin,trimethylolpropane, hexane triol, triethanolamine, diglycerin,pentaerythrytol, trimethylolpropane and hexane triol. They may be usedalone or in combination of two or more.

Examples of the above alkylene oxide include ethylene oxide, propyleneoxide and cyclic ether compounds such as tetrahydrofuran. They may beused alone or in combination of two or more.

The number average molecular weight of the polyether polyol ispreferably 400 to 2,000, more preferably 500 to 1,500, most preferably600 to 1,200 for the same reason as that of the polycarbonate polyol.

The polyether polyol can be acquired industrially as a reagent.Commercially available products thereof include the Excenol (registeredtrademark) series and Emulstar (registered trademark) of Asahi GlassCo., Ltd. and the Adeka Polyether series of ADEKA Corporation.

<Polyester Polyol>

Examples of the polyester polyol include polyester polyols obtained froma condensation reaction between a polyhydric alcohol and a polybasicacid. Examples of the above polyhydric alcohol include ethylene glycol,1,2-propanediol, 1,3-butanediol, 1,4-butanediol,3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3′-dimethylolheptane,1,4-cyclohexane dimethanol, neopentyl glycol,3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol,glycerin and trimethylol propane. They may be used alone or incombination of two or more. Examples of the above polybasic acid includesuccinic acid, adipic acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid, cyclopentanedicarboxylic acid,cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid,terephthalic acid and naphthalene dicarboxylic acid. They may be usedalone or in combination of two or more.

The number average molecular weight of the polyester polyol ispreferably 400 to 2,000, more preferably 500 to 1,500, most preferably600 to 1,200 for the same reason as that of the polycarbonate polyol.

These polyester polyols can be acquired industrially as a reagent.Commercially available products thereof include the Polylite (registeredtrademark) series of DIC Corporation, the Nipporan (registeredtrademark) series of Nippon Polyurethane Industry Co., Ltd., and theMaximol (registered trademark) series of Kawasaki Kasei Chemicals.

<Component A2: Diisocyanate Compound Having Two Isocyanate Groups in theMolecule>

As the above diisocyanate compound (component A2), aliphaticdiisocyanate compounds, alicyclic diisocyanate compounds, aromaticdiisocyanate compounds and mixtures thereof are used. Out of these,aliphatic diisocyanate compounds and/or alicyclic diisocyanate compoundsare preferably used from the viewpoint of weatherability. Preferably,the aliphatic diisocyanate compound accounts for 30 to 100 mass %,particularly 50 to 100 mass % of the component A2 for the same reason asabove.

Examples of the diisocyanate compound which can be preferably used asthe component A2 include aliphatic diisocyanate compounds such astetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate,octamethylene-1,8-diisocyanate and2,2,4-trimethylhexane-1,6-diisocyanate; alicyclic diisocyanate compoundssuch as cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate,cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate,2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornenediisocyanate, isomer mixtures of 4,4′-methylenebis(cyclohexylisocyanate), hexahydrotoluene-2,4-diisocyanate,hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate,hexahydrophenylene-1,4-diisocyanate, 1,9-diisocyanato-5-methylnonane,1,1-bis(isocyanatomethyl)cyclohexane,2-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]-1-methylcyclohexane,2-(3-isocyanatopropyl)cyclohexyl isocyanate and norbornane diisocyanate;and aromatic diisocyanate compounds such as phenyl cyclohexylmethanediisocyanate, isomer mixtures of 4,4′-methylenebis(phenyl isocyanate),toluene-2,3-diisocyanate, toluene-2,4-diisocyanate,toluene-2,6-diisocyanate, phenylene-1,3-diisocyanate,phenylene-1,4-diisocyanate, 1,3-bis(isocyanatomethyl)benzene, xylylenediisocyanate, tetramethyl xylylene diisocyanate, naphthalenediisocyanate, diphenyl ether diisocyanate, 1,3-diisocyanatomethylbenzene, 4,4′-diisocyanato-3,3′-dimethoxy(1,1-biphenyl),4,4′-diisocyanato-3,3′-dimethylbiphenyl, 1,2-diisocyanatobenzene,1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene,2-dodecyl-1,3-diisocyanatobenzene,1-isocyanato-4-[(2-isocyanatocyclohexyl)methyl]2-methylbenzene,1-isocyanato-3-[(4-isocyanatophenyl)methyl]-2-methylbenzene,4-[(2-isocyanatophenyl)oxy]phenyl isocyanate and diphenylmethanediisocyanate.

Of these, at least one diisocyanate compound selected from the groupconsisting of aliphatic diisocyanate compounds and alicyclicdiisocyanate compounds accounts for preferably 30 to 100 mass %, morepreferably 50 to 100 mass % of the diisocyanate compound as thecomponent A2 from the viewpoint of the weatherability of the obtainedpolyurethane urea resin (component (I)) as described above. Preferredexamples of the compound include tetramethylene-1,4-diisocyanate,hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate,2,2,4-trimethylhexane-1,6-diisocyanate, cyclobutane-1,3-diisocyanate,cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate,2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate,isophorone diisocyanate, norbornane diisocyanate, isomer mixtures of4,4′-methylenebis(cyclohexyl isocyanate),hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate,hexahydrophenylene-1,3-diisocyanate andhexahydrophenylene-1,4-diisocyanate. These isocyanate compounds may beused alone or in combination of two or more.

<(B) Polyamine Compound Having at Least Two Amino Groups in theMolecule>

The polyamine compound having at least two amino groups in the molecule(component B) is a polyamine compound having at least two amino groups(—NH₂ or —NH(R). R is an alkyl group, preferably alkyl group having 1 to5 carbon atoms) in the molecule.

The component B serves as a chain extender when the polyurethane urearesin (component (I)) is synthesized. By using the component B as achain extender, a urea bond is introduced into a polyurethane resin toobtain a polyurethane urea resin.

To provide suitable hardness to the obtained polyurethane urea resin(component (I)) and maintain excellent adhesion and heat resistance, themolecular weight of the polyamine compound is preferably 50 to 300, morepreferably 50 to 250, most preferably 100 to 220.

As the polyamine compound as the component B, at least one compoundselected from the group consisting of diamines and triamines may bepreferably used. Examples of the compound which is preferably used asthe polyamine compound in the present invention include isophoronediamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane,1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane,1,5-diaminopentane, 1,6-diaminohexane, piperazine,N,N-bis-(2-aminoethyl)piperazine, bis-(4-aminocyclohexyl)methane,bis-(4-amino-3-butylcyclohexyl)methane, 1,2-, 1,3- and1,4-diaminocyclohexanes, norbornane diamine, hydrazine, dihydrazineadipate, phenylenediamine, 4,4′-diphenylmethane diamine,N,N′-diethylethylene diamine, N,N′-dimethylethylene diamine,N,N′-dipropylethylene diamine, N,N′-dibutylethylene diamine,N-methylethylene diamine, N-ethylethylene diamine,bis(hexamethylene)triamine and 1,2,5-pentanetriamine.

A diamine compound is particularly preferably used as the polyaminecompound from the viewpoints of adhesion and heat resistance. The reasonfor this is assumed as follows. By using the polyamine compound tosynthesize the polyurethane urea resin (component (I)), a urea bond isintroduced with the result that the stiffness of the molecule becomeshigh and a hydrogen bond between molecular chains becomes strong,thereby improving heat resistance. The hydrogen bond between molecularchains becomes strong due to the existence of the urea bond, therebymaking it difficult for oxygen contained in air to be dispersed into thepolyurethane urea resin (component (I)) with the result that the opticaloxidization deterioration of the polyurethane urea resin is suppressed.Further, it is assumed that the reason for the improvement of adhesionis that the hydrogen bond between molecular chains becomes strong due tothe existence of the urea bond, thereby rarely causing the cohesivefracture of the resin.

Out of the above polyamine compounds, isophorone diamine,bis-(4-aminocyclohexyl)methane and norbornane diamine are preferablyused, and bis-(4-aminocyclohexyl)methane is most preferably used fromthe viewpoints of water resistance and stability in a perspirationresistance test.

<(C) Compound Having One Group Able to React with an Isocyanate Group inthe Molecule>

To synthesize the above polyurethane urea resin, a compound having onegroup able to react with an isocyanate group in the molecule (componentC) is used. By using this component C, a polyurethane urea resin havinga capped end of the molecular chain is obtained. Examples of the groupable to react with an isocyanate group include amino group (—NH₂ groupand —NH(R) group), hydroxyl group (—OH group), mercapto group (—SHgroup: thiol group), carboxyl group [—C(═O)OH group] and acid chloridegroup [—C(═O)OCl group]. Out of the above components C, afunctionality-imparting compound having at least one piperidinestructure in the molecule is preferred. As the functionality-impartingcompound, a compound having a hindered phenol structure, triazinestructure or benzotriazole structure in place of the piperidinestructure may be used. What has the most excellent effect is afunctionality-imparting compound having a piperidine structure.

By using this functionality-imparting compound, a piperidine structurecan be introduced into the polyurethane urea resin (component (I)) withthe result that a polyurethane urea resin having excellent opticalstabilization, oxidation prevention and ultraviolet absorbing properties(component (I)) can be obtained.

A detailed description is subsequently given of the compound having apiperidine structure as a typical example of the compound used as thecomponent C.

<Compound Having a Piperidine Structure>

As the compound having a piperidine structure used as the component C inthe polyurethane urea resin, a compound having a structure representedby the following formula (i) in the molecule can be advantageously used.

In the above formula, R¹, R², R³ and R⁴ are each independently an alkylgroup having 1 to 4 carbon atoms, particularly preferably methyl group.A compound having a group able to react with an isocyanate group at thenitrogen atom or the 4-position carbon atom of the above piperidinering, that is, a compound having a group bonded to any one of the twobonds in the above formula as the group able to react with an isocyanategroup is the compound having a piperidine structure. A more specificcompound is described hereinbelow.

As the compound which can introduce a piperidine structure into the endof the polyurethane urea resin as the component I in the presentinvention out of the compounds used as the component C in the presentinvention, a compound represented by the following formula (1) ispreferred.

In the above formula, R¹, R², R³ and R⁴ are as defined in the aboveformula (i), R⁵ is an alkyl group having 1 to 10 carbon atoms orhydrogen atom, R⁶ is an alkylene group having 1 to 20 carbon atoms orpolymethylene group having 3 to 20 carbon atoms, “a” is 0 or 1, and X isa group able to react with an isocyanate group.

In the above formula (1), R¹, R², R³ and R⁴ are each independently analkyl group having 1 to 4 carbon atoms. Preferably, four alkyl groupsare all methyl groups.

R⁵ is an alkyl group having 1 to 10 carbon atoms or hydrogen atom. Fromthe viewpoint of acquisition ease, it is preferably an alkyl grouphaving 1 to 4 carbon atoms or hydrogen atom. Since R¹ to R⁴ are alkylgroups having 1 to 4 carbon atoms, even when R⁵ is a hydrogen atom, thenitrogen atom bonded to R⁵ does not react with an isocyanate group dueto the influence of steric hindrance.

R⁶ is an alkylene group having 1 to 20 carbon atoms or polymethylenegroup having 3 to 20 carbon atoms, preferably an alkylene group having 1to 10 carbon atoms or polymethylene group having 3 to 10 carbon atoms.“a” is the number of R⁶, s. When “a” is 0, it should be understood thatX is directly bonded to the piperidine ring.

X is a group able to react with an isocyanate group, preferably aminogroup, hydroxyl group, carboxyl group or thiol group. It is particularlypreferably an amino group or hydroxyl group from the viewpoints ofreactivity with an isocyanate group and acquisition ease.

Examples of the compound represented by the above formula (1) include1,2,2,6,6-pentamethyl-4-hydroxypiperidine,1,2,2,6,6-pentamethyl-4-aminopiperidine,2,2,6,6-tetramethyl-4-hydroxypiperidine,2,2,6,6-tetramethyl-4-aminopiperidine,1,2,2,6,6-pentamethyl-4-aminomethylpiperidine and1,2,2,6,6-pentamethyl-4-aminobutylpiperidine.

<Other Components C>

Besides the above compound having a piperidine structure which is usedto improve weatherability, ordinary amines, alcohols, thiols andcarboxylic acids may be used as the component C. Since these compoundshave one group able to react with an isocyanate group in the molecule,they can deactivate the end of the polyurethane urea resin as thecomponent I.

Out of the other components C used in the present invention, compoundsrepresented by the following formulas (2) and (3) are preferred.

In the above formula, R⁷ is an alkyl group having 1 to 20 carbon atoms,aryl group, aralkyl group, alkyloxycarbonyl group or hydrogen atom.

R⁸ is an alkyl group having 1 to 20 carbon atoms, aryl group, aralkylgroup or ester group.

When a compound in which R⁷ is a hydrogen atom is used as the componentC, the end of the polyurethane urea resin as the component (I) is a—NH(R⁸) group which does not react with another polymer and anisocyanate compound substantially. Therefore, the —NH(R⁸) group is not agroup able to react with an isocyanate group.

In the above formula (2), R⁷ is an alkyl group having 1 to 20 carbonatoms, aryl group, aralkyl group, alkyloxycarbonyl group or hydrogenatom. R⁷ is particularly preferably an alkyl group having 1 to 10 carbonatoms, aryl group, aralkyl group, alkyloxycarbonyl group or hydrogenatom. The above aryl group and aralkyl group may have an alkyl grouphaving 1 to 5 carbon atoms or halogen atom as a substituent.

Preferred examples of R⁷ include methyl group, ethyl group, normalpropyl group, isopropyl group, normal butyl group, tert-butyl group,pentyl group, hexyl group, heptyl group, octyl group,1,1,3,3-tetramethylbutyl group, phenyl group, benzyl group,1,1-dimethylbenzyl group, carboxymethyl group, carboxyethyl group,carboxypropyl group and hydrogen atom.

R⁸ is an alkyl group having 1 to 20 carbon atoms, aryl group, aralkylgroup or alkyloxycarbonyl group. R⁸ is particularly preferably an alkylgroup having 1 to 10 carbon atoms, aryl group, aralkyl group oralkyloxycarbonyl group. The above aryl group may have an alkyl grouphaving 1 to 5 carbon atoms or halogen atom as a substituent.

Preferred examples of R⁸ include methyl group, ethyl group, normalpropyl group, isopropyl group, normal butyl group, tert-butyl group,pentyl group, hexyl group, heptyl group, octyl group,1,1,3,3-tetramethylbutyl group, phenyl group, benzyl group,1,1-dimethylbenzyl group, carboxymethyl group, carboxyethyl group andcarboxypropyl group.

Compounds represented by the following formula (3) may also beadvantageously used.

Z—R⁹  (3)

In the above formula, R⁹ is an alkyl group having 1 to 20 carbon atoms,aryl group, aralkyl group or alkyloxycarbonyl group, and Z is a hydroxylgroup, carboxyl group or thiol group.

In the above formula (3), R⁹ is an alkyl group having 1 to 20 carbonatoms, aryl group, aralkyl group or alkyloxycarbonyl group, preferablyan alkyl group having 1 to 10 carbon atoms, aryl group, aralkyl group oralkyloxycarbonyl group. The aryl group and the aralkyl group may have analkyl group having 1 to 5 carbon atoms or halogen atom as a substituent.The preferred group is an alkyl group having 1 to 5 carbon atoms, phenylgroup or phenyl group having a halogen atom. Preferred examples of R⁹include methyl group, ethyl group, normal propyl group, isopropyl group,normal butyl group, tert-butyl group, pentyl group, hexyl group, heptylgroup, octyl group, 1,1,3,3-tetramethylbutyl group, phenyl group, benzylgroup, 1,1-dimethylbenzyl group, carboxymethyl group, carboxyethyl groupand carboxypropyl group.

Z in the above formula (3) is a group able to react with an isocyanategroup, more specifically, hydroxyl group, carboxyl group or thiol group,preferably hydroxyl group.

Examples of the compounds represented by the above formulas (2) and (3)include amines such as methylamine, ethylamine, propylamine,isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine,heptylamine, 4-heptylamine, octylamine, 1,1-dipropylbutylamine,phenylamine, benzylamine, dimethylamine, diethylamine, dipropylamine,diisopropylamine, dibutylamine, di-tert-butylamine, dipentylamine,dihexylamine, diheptylamine, dioctylamine, methylethylamine,methylbutylamine, methylpentylamine, methylhexylamine,methylheptylamine, methyloctylamine, ethylpropylamine, ethylbutylamine,ethylpentylamine, ethylhexylamine, ethylheptylamine, ethyloctylamine,propylbutylamine, isopropylbutylamine, propylpentylamine,propylhexylamine, propylheptylamine and propyloctylamine; alcohols suchas methanol, ethanol, propanol, isopropanol, butanol, 2-butanol,tert-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octylalcohol, nonyl alcohol, decanol and 2-decanol; thiols such asmethanethiol, ethanethiol, 1-propanethiol, 2-propanethiol,1-butanethiol, 2-butanethiol, propanethiol, hexanethiol, heptanethiol,octanethiol, dodecanethiol, 2-methyl-1-butanethiol,2-methylpropanethiol, 3-methyl-2-butenethiol, 1,1-dimethylheptanethiol,cyclohexanethiol, cyclopentanethiol, benzenethiol, benzene methanethioland 2,6-dimethylbenzenethiol; and carboxylic acids such as acetic acid,propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoicacid, octanoic acid, nonanoic acid, decanoic acid and dodecanoic acid.

The above components C may be used alone or in combination of two ormore. A compound having a piperidine structure is preferably used toimprove the durability of the polyurethane urea resin.

<Contents of Components A1, A2, B and C in Polyurethane Urea Resin>

In the present invention, the ratio of the above components constitutingthe polyurethane urea resin (component I) in the photochromiccomposition of the adhesive layer, that is, the components A1, A2, B andC is suitably determined in consideration of the intended use of thepolyurethane urea resin. From the viewpoint of balance between the heatresistance and adhesive strength of the obtained polyurethane urearesin, the following ratio is preferred. That is, when the total numberof moles of the hydroxyl group contained in the component A1 isrepresented by n1, the total number of moles of the isocyanate groupcontained in the component A2 is represented by n2, the total number ofmoles of the amino group contained in the component B is represented byn3, and the total number of moles of the group able to react with anisocyanate group contained in the component C (specifically, aminogroup, hydroxyl group, mercapto group and/or carboxyl group) isrepresented by n4, preferably n1:n2:n3:n4=0.4 to 0.8/1.0/0.19 to0.59/0.01 to 0.2, particularly preferably n1:n2:n3:n4=0.45 to0.75/1.0/0.23 to 0.53/0.02 to 0.15, most preferably n1:n2:n3:n4=0.65 to0.75/1.0/0.23 to 0.33/0.02 to 0.1. n1 to n4 can be each obtained as aproduct of the number of moles in use of a compound as each componentand the number of groups existent in one molecule of the compound.

It is preferred that the above polyurethane urea resin (component (I))should not have a reactive group at the end. It is particularlypreferred that the polyurethane urea resin should be deactivated toprevent the isocyanate group from remaining at the end. To this end, itis preferred to produce the polyurethane urea resin by mixing togetherthe above components to ensure n2=n1+n3+n4. When the total number ofmoles of n1, n3 and n4 (n1+n3+n4) is larger than n2, unreactedcomponents A1, B and C can be removed by re-precipitation.

<Polyurethane Urea Resin Having a Polydispersity (Weight AverageMolecular Weight/Number Average Molecular Weight Ratio) of 1.6 to 2.4>

In the present invention, as the polyurethane urea resin used in thephotochromic composition, a polyurethane urea resin having apolydispersity (weight average molecular weight/number average molecularweight ratio) of 1.6 to 2.4 is preferably used. When a laminate ismanufactured by bonding polycarbonate optical sheets or films by meansof an adhesive layer composed of a photochromic composition comprising apolyurethane urea resin having this narrow range of polydispersity, theobtained laminate exhibits excellent adhesion, especially excellentadhesion at a high temperature, and excellent photochromic properties.Further, the obtained laminate has high perspiration resistance. Thatis, even after it is brought into contact with artificial perspiration,the laminate exhibits excellent adhesion. Although the details of thereason that this effect is obtained are unknown, the inventors of thepresent invention assume it as follows. That is, since thepolydispersity (weight average molecular weight/number average molecularweight ratio) is 1.6 to 2.4, the content of a low-molecular weightpolyurethane urea can be reduced, thereby stabilizing heat resistance.Further, the reduction of physical interaction between molecules, thatis, intertwining between the molecules of a polymer chain due to theinfluence of the low-molecular weight polyurethane urea can besuppressed and fracture, that is, cohesive fracture in the polyurethaneurea layer can be suppressed when the polyurethane urea resin is used inthe adhesive layer, thereby improving adhesion.

As the polydispersity becomes lower, that is, closer to 1.0, the effectof the present invention tends to appear more markedly. It issubstantially difficult to obtain a polyurethane urea resin having apolydispersity of less than 1.6 with an industrial-scale productionmethod. When the polydispersity exceeds 2.4, the softening starttemperature tends to become low due to the influence of thelow-molecular weight polyurethane urea resin. Therefore, as comparedwith a resin having a narrow polydispersity range, this polyurethaneurea resin tends to deteriorate in heat resistance and adhesion at ahigh temperature. Due to the influence of a high-molecular weightpolyurethane urea resin, viscosity rises considerably at the time ofdissolving in an organic solvent as compared with the resin having anarrow polydispersity range, thereby making coating difficult. From theviewpoints of excellent adhesion, heat resistance and coatability, thepolydispersity of the polyurethane urea resin of the present inventionis more preferably 1.8 to 2.2.

The molecular weight of the polyurethane urea resin of the presentinvention is not particularly limited if the polydispersity satisfiesthe above range. From the viewpoints of adhesive strength, heatresistance and perspiration resistance, it is recommended that thenumber average molecular weight of the polyurethane urea resin should bepreferably 5,000 to 100,000, more preferably 8,000 to 50,000,particularly preferably 10,000 to 40,000.

The number average molecular weight and the weight average molecularweight of the above polyurethane urea resin are values obtained bymeasuring a 1.0% dimethyl formamide (DMF) solution of a polyurethaneurea resin sample by using a gel permeation chromatograph (GPC) in termsof polyethylene oxide, two Shodex KD-806M columns connected in series(manufactured by Showa Denko K.K.), a LiBr (10 mmol/L)/DMF solution asan elute and a RI detector at a flow rate of 1 ml/min and calculatingwith the Empower Personal GPC Option GPC analyzing software of NihonWaters K.K. The polydispersity is a weight average molecularweight/number average molecular weight ratio and a value calculated fromnumber average molecular weight and weight average molecular weightobtained by the above method.

To obtain the polyurethane urea resin (component I) of the presentinvention by reacting the above components A1, A2 and B and optionallythe component C, they should be reacted with one another to achieve theabove range of polydispersity, and so-called “one-shot method” or“prepolymer method” may be employed. However, to obtain the polyurethaneurea resin efficiently by controlling the polydispersity, the prepolymermethod is preferred. According to the production method which will bedescribed hereinafter, the polyurethane urea resin having the aboverange of polydispersity can be easily produced.

The above polyurethane urea resin (component (I)) may also be used inthe adhesive layer containing no photochromic compound.

<Method of Producing Polyurethane Urea Resin> <Method of ProducingUrethane Prepolymer (A)>

In the present invention, the polyurethane urea resin used in thephotochromic composition can be generally produced from a reactionbetween a urethane prepolymer and a polyamine such as diamine. Theurethane prepolymer (component A) can be produced by reacting the abovepolyol compound (component A1) with the above diisocyanate compound(component A2) (to be also referred to as “prepolymer reaction”hereinafter).

The urethane prepolymer (component A) of the present invention ispreferably a urethane prepolymer having an isocyanate group at the endby making n1:n2=0.4/1.0 to 0.8/1.0 when the total number of moles of thehydroxyl group contained in the component A1 is represented by n1 andthe total number of moles of the isocyanate group contained in thecomponent A2 is represented by n2.

The addition order of the component A1 and the component A2 when theyare reacted with each other is not particularly limited. The componentA1 and the component A2 may be added additionally during the reaction asrequired.

The reaction between the component A1 and the component A2 is preferablycarried out in the presence or absence of an organic solvent in an inertgas atmosphere such as nitrogen or argon at a reaction temperature of 70to 130° C. When the reaction temperature is lower than 70° C., thereaction is not completed and when the reaction temperature is higherthan 130° C., part of the component A1 decomposes and therefore apolyurethane urea resin having desired physical properties cannot beobtained. The reaction time which changes according to the charge ratioof the component A1 and the component A2 and the reaction temperaturemay be set to a range of 0.5 to 24 hours.

As the organic solvent, organic solvents such as acetone, methyl ethylketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane,toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and tetrahydrofuran (THF) maybe used. These organic solvents may be used alone or in combination oftwo or more.

When the organic solvent is used, the amount thereof is preferably notmore than 200 parts by mass based on 100 parts by mass of the total ofthe component A1 and the component A2. When the amount of the organicsolvent is larger than 200 parts by mass, the reaction time between thecomponent A1 and the component A2 becomes long and part of the componentA1 may decompose.

To prevent a reaction between the isocyanate group contained in thediisocyanate compound and water which is an impurity during thereaction, the reaction reagents and the solvent are preferablydehydrated and fully dried in advance. To carry out the above reaction,a catalyst such as dibutyltin dilaurate, dimethyl imidazole,triethylenediamine, tetramethyl-1,6-hexadiamine,tetramethyl-1,2-ethanediamine or 1,4-diazabicyclo[2.2.2]octane may beused. The amount of the catalyst is preferably 0.001 to 1 part by massbased on 100 parts by mass of the total of the component A.

<Method of Producing Polyurethane Urea Resin>

The polyurethane urea resin can be produced from a reaction between theurethane prepolymer and a polyamine such as diamine. When the urethaneprepolymer is produced by the above method, the polyamine compound asthe component B is added to the reaction solution after the aboveprepolymerization reaction, thereby making it possible to produce thepolyurethane urea resin continuously.

Other reaction conditions in the above method of producing thepolyurethane urea resin are suitably determined in consideration ofproduction equipment. In general, the reaction can be carried out in thepresence of an organic solvent in an inert gas atmosphere such asnitrogen or argon as required at a reaction temperature of −20 to 40°C., preferably −10 to 20° C.

Examples of the organic solvent used in the production of the abovepolyurethane urea resin include alcohol-based organic solvents such asacetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone,cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butylacetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO),tetrahydrofuran (THF), methanol, ethanol, isopropyl alcohol, t-butanol,2-butanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol mononormal propyl ether, ethyleneglycol monoisopropyl ether, ethylene glycol monobutyl ether, ethyleneglycol mono-t-butyl ether, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, propylene glycol mononormal propyl ether,propylene glycol monoisopropyl, propylene glycol mononormal butyl etherand propylene glycol mono-t-butyl ether. These organic solvents may beused alone or in combination of two or more.

The amount of the above organic solvent is preferably 130 to 800 partsby mass, more preferably 150 to 500 parts by mass based on 100 parts bymass of the total of the finally obtained polyurethane urea resin fromthe viewpoints of carrying out the reaction efficiently and theinfluence of the remaining organic solvent.

To prevent a reaction between the isocyanate group and water as animpurity in the reaction system during the reaction, the reactionreagents and the organic solvent are preferably dehydrated and fullydried in advance. To carry out the above reaction, a catalyst such asdibutyltin dilaurate, dimethyl imidazole, triethylene diamine,tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine or1,4-diazabicyclo[2,2,2]octane may be newly added. When the catalyst isused in the prepolymer reaction, it may be used as it is without beingremoved. The amount of the catalyst is preferably 0.001 to 1 part bymass based on 100 parts by mass of the total of the polyurethane urearesin,

To synthesize the above polyurethane urea resin (component (I)), acompound having one group able to react with an isocyanate group in themolecule (component C) is used. By using this component C, apolyurethane urea resin having the capped end of the molecular chain isobtained.

As means for obtaining the polyurethane urea resin having the capped endof the molecular chain (may also be referred to as “terminalmodification reaction” hereinafter), there is a preferred method inwhich the component C which has been diluted with an organic solvent asrequired is added dropwise to a reaction solution containing thepolyurethane urea resin having an isocyanate group at the end dissolvedin an organic solvent after the end of the reaction between thecomponent A and the component B. When the alcohol-based organic solventadded during the reaction between the component A and the component B isused as the component C for the terminal modification reaction, thecomponent C does not need to be newly added.

The above terminal modification reaction is carried out in the presenceof an organic solvent in an inert gas atmosphere such as nitrogen orargon as required. The reaction temperature is −20 to 30° C. which isthe same temperature as that for the reaction between the component Aand the component B when the group able to react with an isocyanategroup contained in the component C is an amino group. When the groupable to react with the isocyanate group contained in the component C isnot an amino group, the reaction temperature is preferably higher than30° C. and not higher than 130° C. as the reaction rate with theisocyanate group is low.

The reaction time is 0.5 to 3 hours when the group able to react withthe isocyanate group contained in the component C is an amino group and1 to 24 hours when the group able to react with the isocyanate groupcontained in the component C is not an amino group.

As the organic solvent, the same organic solvent as that used in theabove prepolymer reaction and the reaction between the component A andthe component B may be used. As a matter of course, the terminalmodification reaction may be carried out while the organic solvent usedin the above prepolymer reaction and the reaction between the componentA and the component B is contained.

The amount of the organic solvent in the terminal modification reactionis preferably 130 to 800 parts by mass based on 100 parts by mass of thefinally obtained component A.

To prevent a reaction between the isocyanate group and water as animpurity in the reaction system during the reaction, the reactionreagents and the organic solvent are preferably dehydrated and fullydried in advance. To carry out the above reaction, a catalyst such asdibutyltin dilaurate, dimethyl imidazole, triethylene diamine,tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine or1,4-diazabicyclo[2,2,2]octane may be newly added. When the catalyst isused till the prepolymer reaction, it may be used as it is without beingremoved. The amount of the catalyst is preferably 0.001 to 1 part bymass based on 100 parts by mass of the total of the component A.

<Method of Producing Polyurethane Urea Resin Having a Polydispersity(Weight Average Molecular Weight/Number Average Molecular Weight Ratio)of 1.6 to 2.4>

To produce the polyurethane urea resin having a polydispersity (weightaverage molecular weight/number average molecular weight ratio) of 1.6to 2.4 as described above, the time (θ_(M)) for mixing together thecomponent A and the component B completely is set to preferably not morethan 30 seconds, more preferably not more than 15 seconds when theurethane prepolymer (component A) and the polyamine compound (componentB) are reacted with each other, thereby making it possible to obtain apolyurethane urea resin having a polydispersity (weight averagemolecular weight/number average molecular weight) of 1.6 to 2.4.

The complete mixing time (θ_(M)) is an index indicative of mixingcharacteristics in a stirring tank (such as a reaction vessel) andobtained from “n·θ_(M)−Re curve” which shows the relationship betweenn·θ_(M) (n is the revolution of a stirring blade (1/sec)) and Re(Reynolds number; index indicative of the turbulence of a liquid). Asfor the complete mixing time (θ_(M)) and the n·θ_(M)−Re curve, refer,for example, to “Technical Report Vol. 35, No. 104, p. 74-78, August,1987 of Sumitomo Heavy Industries, Ltd.”, JP-A 61-200842 and JP-A6-312122.

As means for setting the complete mixing time (θ_(M)) to not more than30 seconds, any suitable method is employed. For example, a method inwhich a baffle plate is installed in a stirring tank (such as a reactionvessel) to cause turbulence, or a method in which an arbitrary suitablestirring blade is used is employed. Examples of the suitable stirringblade include max blend blade and full-zone blade.

When the urethane prepolymer is produced by the above method, thecomponent B is added to the reaction solution after theprepolymerization reaction, thereby making it possible to produce thepolyurethane urea resin continuously.

Other reaction conditions in the method of producing the polyurethaneurea resin having the above range of polydispersity are suitablydetermined in consideration of production equipment. From the viewpointof obtaining a polyurethane urea resin having the narrow range ofpolydispersity, the reaction is preferably carried out in the presenceof an organic solvent in an inert gas atmosphere such as nitrogen orargon as required at a reaction temperature of preferably −20 to 40° C.,more preferably −10 to 20° C. When the reaction temperature is lowerthan −20° C., viscosity rises in the latter half stage of a chainextension reaction with the result that stirring may becomeunsatisfactory. When the reaction temperature is higher than 40° C., aurea bond formation reaction becomes fast, a heterogeneous reaction mayoccur as the component A and the component B react with each other uponcontact with each other, and polydispersity tends to become wide. Areaction time at the above reaction temperature of 0.5 to 3 hourssuffices.

A description is subsequently given of the photochromic compound (II)used in the present invention.

<(II) Photochromic Compound>

In the present invention, as the photochromic compound (II), knownphotochromic compounds such as chromene compounds, fulgimide compounds,spirooxazine compounds and spiropyran compounds may be used. They may beused alone or in combination of two or more.

Examples of the above fulgimide compounds, spirooxazine compounds,spiropyran compounds and chromene compounds include compounds disclosedby JP-A 2-28154, JP-A 62-288830, WO94/22850 and WO96/14596.

Out of these photochromic compounds, at least one chromene compoundhaving an indeno(2,1-f)naphtho(2,1-b)pyran skeleton is preferably usedfrom the viewpoints of photochromic properties such as color opticaldensity, initial coloration, durability and fading speed. A chromenecompound having a molecular weight of not less than 540 is morepreferred as it is particularly excellent in color optical density andfading speed.

Examples of the photochromic compound which can be particularlypreferably used in the present invention are given below.

In the present invention, the amount of the photochromic compound (II)is preferably 0.1 to 20.0 parts by mass based on 100 parts by mass ofthe polyurethane urea resin (I) from the viewpoints of photochromicproperties. When the above amount is too small, satisfactory coloroptical density and durability may not be obtained. When the aboveamount is too large, depending on the type of the photochromic compound,the photochromic compound hardly dissolves in the photochromiccomposition, whereby the composition tends to deteriorate in homogeneityand bonding strength (adhesive strength). To fully keep high adhesion tothe polycarbonate optical sheets or films of the present invention whileretaining photochromic properties such as color optical density anddurability, the amount of the photochromic compound (II) is preferably0.5 to 10.0 parts by mass, particularly preferably 1.0 to 7.0 parts bymass based on 100 parts by mass of the polyurethane urea resin (I). Whenthe photochromic composition is mixed with the component (III) whichwill be described hereinafter, the amount of the photochromic compound(II) is preferably 0.1 to 20.0 parts by mass, more preferably 0.5 to10.0 parts by mass, much more preferably 1.0 to 7.0 parts by mass basedon 100 parts by mass of the total of the polyurethane urea resin (I) andthe component (III).

A description is subsequently given of the polyisocyanate compoundhaving at least two isocyanate groups in the molecule (III) which ispreferably used in the photochromic composition of the presentinvention.

<(III) Polyisocyanate Compound Having at Least Two Isocyanate Groups inthe Molecule>

The adhesive or closely adhesive strength of the laminate of the presentinvention can be further improved when the photochromic composition usedin the adhesive layer comprises a product obtained by reacting the abovepolyurethane urea resin (I) with the polyisocyanate compound having atleast two isocyanate groups in the molecule (III) (to be simply referredto as “component (III)” hereinafter).

When at least two isocyanate groups are contained in the molecule of thecomponent (III), the component (III) reacts with the polyurethane urearesin (I), thereby making it possible to produce a polyurethane urearesin having a crosslinked structure at the time of forming the adhesivelayer composed of the photochromic composition. Or/further, anisocyanate group(s) contained in the molecule of the component (III)hydrolyze(s) to become an amine which reacts with an isocyanate group(s)contained in the molecule of another component (III), thereby making itpossible to produce a urea resin in the component (I). It is consideredthat the heat resistance of the polyurethane urea resin improves andcohesive fracture hardly occurs since this crosslinked structure and/orthe new urea resin are/is formed in the polyurethane urea resin (I).Therefore, it is considered that the effect of improving adhesionbecomes large. This effect is greater than when an ordinary two-liquidpolyurethane resin is used. However, when operation ease and theviscosity and storage stability of the obtained photochromic compositionare taken into consideration, the component (III) preferably has 2 to 3isocyanate groups in the molecule.

To form an adhesive layer composed of the photochromic composition andhaving excellent adhesion, compounds having an isocyanate group bondedto a secondary carbon are preferably used as the component (III). Theymay be used alone or in combination of two or more. The advantageobtained by using the component (III) having an isocyanate group bondedto a secondary carbon is the great effect of improving heat resistanceand adhesion.

In addition, polyisocyanate compounds having a relatively flexible group(group having high mobility) and two isocyanate groups in the moleculemay be used as the above component (III). Heat resistance and adhesioncan be improved by using at least one polyisocyanate compound (may besimply referred to as “component (IIIB)” hereinafter) selected from thegroup consisting of hexamethylene diisocyanate, burette compounds ofhexamethylene diisocyanate, isocyanurate compounds of hexamethylenediisocyanate and adduct compounds of hexamethylene diisocyanate. Thepolyisocyanate compounds (IIIB) having a relatively flexible group(group having high mobility) and two isocyanate groups in the moleculemay be used alone or in combination of two or more.

In the present invention, the effect of improving heat resistance andadhesion when the component (III) is added to the component (I) isobtained after a laminate is produced by using the photochromiccomposition comprising these. Stated more specifically, it is consideredthat, after a laminate is produced by using a photochromic compositioncomprising the component (I) and the component (III), the effect ofimproving heat resistance and adhesion is obtained by supplying heat andmoisture. That is, one isocyanate group of the component (III) reactswith the urethane bond or urea bond of the component (I) by heat. Then,it is considered that, in a moisture reaction (reaction in the presenceof water), the remaining isocyanate group(s) of the component (III)bonded to the component (I) and an isocyanate group(s) of a component(III) remaining free hydrolyze by moisture to produce an amine, therebycausing a crosslinking reaction. Or/further, it is considered that aisocyanate group(s) of the component (III) remaining free hydrolyze(s)by moisture to produce an amine which reacts with an isocyanate group(s)of another component (III) remaining free to produce a new urea resin inthe component (I).

By using at least one compound having an isocyanate group bonded to asecondary carbon (component (IIIA)) and a polyisocyanate compound havinga relatively flexible group (group having high mobility) and twoisocyanate groups in the molecule in combination as the above component(III), adhesion can be further improved.

Examples of the preferred compound having an isocyanate group bonded toa secondary carbon (component IIIA) as the above component (III) includeisomer mixtures of 4,4′-methylenebis(cyclohexyl isocyanate),cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate,cyclohexane-1,4-diisocyanate, hexahydrotoluene-2,4-diisocyanate,hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate,hexahydrophenylene-1,4-diisocyanate and trimers of isophoronediisocyanate (isocyanurate compounds). Out of these, isomer mixtures of4,4′-methylenebis (cyclohexyl isocyanate) are preferably used.

Preferred examples of the polyisocyanate compound having a relativelyflexible group (group having high mobility) and two isocyanate groups inthe molecule include hexamethylene diisocyanate, burette compounds ofhexamethylene diisocyanate, isocyanurate compounds of hexamethylenediisocyanate, and adduct compounds of hexamethylene diisocyanate(component (IIIB)). Out of the components (IIIB), a polyisocyanatecompound selected from the group consisting of burette compounds ofhexamethylene diisocyanate and isocyanurate compounds of hexamethylenediisocyanate is preferably used.

Although the above component (IIIA) and the above component (IIIB) maybe used alone, they are preferably used in combination to furtherimprove adhesion. The above component (IIIA) and the above component(IIIB) are particularly preferably used in combination. When they areused in combination, the amount of the component (IIIB) is preferably 20to 150 parts by mass based on 100 parts by mass of the component (IIIA)to enhance the effect. To further improve adhesion, the amount of thecomponent (IIIB) is preferably 20 to 100 parts by mass, more preferably30 to 80 parts by mass based on 100 parts by mass of the above component(IIIA).

In the photochromic composition used in the laminate of the presentinvention, the molecular weight of the component (III) is notparticularly limited but preferably lower than 1,000. When the molecularweight of the component (III) is not lower than 1,000, the heatresistance and film strength of the adhesive layer composed of theobtained photochromic composition tend to deteriorate. This isconsidered that when the component (III) having a high molecular weightis used, the number of bonds between isocyanate groups tends to increaseand even when a crosslinked structure is formed, the distance betweencrosslink points becomes long with the result that heat resistance doesnot improve much and therefore, adhesion does not improve much as well.Therefore, the molecular weight of the component (III) is preferablylower than 1,000, more preferably not higher than 800, most preferablynot higher than 500. This component (III) is preferably not a polymer asdescribed above. Therefore, the molecular weight of the component (III)is the molecular weight of the component (III) itself. The lower limitof the molecular weight of the component (III) is the molecular weightof the individual compound and not particularly limited but preferably100.

In the laminate of the present invention, the amount of the component(III) in the photochromic composition is preferably 4.0 to 20.0 parts bymass based on 100 parts by mass of the component (I) from the viewpointsof adhesion, heat resistance, perspiration resistance and photochromicproperties. When the amount of the component (III) falls within thisrange, the obtained photochromic composition exhibits an excellenteffect. When the above amount is too small, the effect of improvingadhesion and heat resistance may not be obtained. When the amount is toolarge, the adhesive layer obtained from the photochromic composition maybecome cloudy, adhesion may deteriorate, and the durability ofphotochromic compound may degrade. To improve adhesion to an opticalsubstrate such as a plastic film while retaining photochromic propertiessuch as color optical density and durability, the amount of thecomponent (III) is preferably 6.0 to 17.5 parts by mass, more preferably7.0 to 15.0 parts by mass based on 100 parts by mass of the polyurethaneurea resin (I). When a plurality of components (III) are used, the totalamount of the components (III) should satisfy the above range.

The amount of the isocyanate group of the component (III) is preferably1.0 to 10.0 parts by mass, more preferably 1.5 to 6.0 parts by mass,most preferably 2.0 to 5.0 parts by mass based on 100 parts by mass ofthe component (I). The amount of the isocyanate group can be obtainedfrom the molecular weight of the component (III), the number ofisocyanate groups per molecule and the molecular weight of theisocyanate group. As a matter of course, when a plurality of components(III) are used, the total amount of the isocyanate groups of thecomponents (III) should satisfy the above amount of the isocyanategroup.

The heat resistance of a reaction product between the polyurethane urearesin (I) and the component (III) is preferably 60 to 200° C., morepreferably 100 to 200° C., much more preferably 100 to 190° C.,particularly preferably 120 to 190° C., most preferably 150 to 190° C.from the viewpoints of (i) the physical properties of a laminateobtained by attaching polycarbonate optical sheets or films and a thirdoptical sheet or film which will be described hereinafter, (ii)processing stability when an optical article is produced from theobtained laminate by bending and injection molding, (iii) the adhesionof the obtained laminate and (iv) workability at the time of applying ahard coat solution and curing it when a hard coat layer is formed on thesurface of the laminate or optical article. Heat resistance in thepresent invention means a softening point measured by using athermomechanical measuring instrument (TMA120C of Seiko InstrumentsInc.) under the following conditions.

[Measuring Conditions] Temperature Elevation Rate: 10° C./Min,Measurement Temperature Range: 30 to 200° C., Probe: Needle Probe Havingan End Diameter of 0.5 mm<Characteristic Properties of PreferredPhotochromic Composition>

To make the laminate of the present invention exhibit excellent adhesionand photochromic properties, the heat resistance of the adhesive layercomposed of the above photochromic composition is preferably not lowerthan 100° C.

When the above photochromic composition does not comprise the abovecomponent (III), the heat resistance of the above polyurethane urearesin (I) is preferably not lower than 100° C., more preferably 100 to190° C.

To make the laminate of the present invention exhibit excellentcharacteristic properties, the above photochromic composition preferablycomprises the polyurethane urea resin (I) having a heat resistance of80° C. or higher to lower than 120° C., the component (III) and thephotochromic compound (II). The heat resistance of the adhesive layercomposed of the photochromic composition is preferably not lower than100° C., more preferably 100 to 190° C., much more preferably 120 to190° C., particularly preferably 150 to 190° C.

The polyurethane urea resin (I) having a heat resistance of 80° C. orhigher to lower than 120° C. is considered as soft. By using thispolyurethane urea resin (I) as a base resin, excellent photochromicproperties can be obtained while certain heat resistance is retained.Further, it is considered that a composition comprising the softpolyurethane urea resin (I) and the above component (III) has improvedadhesion to the polarizing film layer, thereby improving adhesion toanother optical film (sheet). In addition, since the effect of improvingheat resistance and adhesion by adding the component (III) is obtainedafter the production of the laminate as described above, a laminatehaving excellent characteristic properties is obtained. The heatresistance of the adhesive layer composed of the photochromiccomposition in the laminate is preferably not lower than 100° C., morepreferably 100 to 190° C., much more preferably 120 to 190° C.,particularly preferably 150 to 190° C. as described above.

<Other Components>

Additives such as organic solvent, surfactant, antioxidant, radicalscavenger, ultraviolet stabilizer, ultraviolet absorbent, release agent,coloring inhibitor, antistatic agent, fluorescent dye, dye, pigment,aroma chemical and plasticizer may be added to the photochromiccomposition used in the laminate of the present invention in order toimprove the durability, color development speed and fading speed of thephotochromic compound (II) and film forming properties. Any knowncompounds may be used as the additives.

Examples of the organic solvent include alcohols such as methanol,ethanol, n-propanol, i-propanol, 2-pentanol, 3-pentanol,3-methyl-2-butanol, 4-methyl-2-pentanol, n-butanol, t-butanol,2-butanol, t-pentyl alcohol and 2,2,2-trifluoroethanol; polyhydricalcohol derivatives such as ethylene glycol monomethyl ether, ethyleneglycol monoisopropyl ether, ethylene glycol monoethyl ether, ethyleneglycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethyleneglycol mono-t-butyl ether, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, propylene glycol-n-butyl ether and ethyleneglycol dimethyl ether; diacetone alcohol; ketones such as methyl ethylketone, diethyl ketone, n-propyl methyl ketone, methyl isobutyl ketone,diisopropyl ketone and n-butylmethyl ketone; toluene; hexane; heptane;acetates such as ethyl acetate, 2-methoxyethyl acetate and 2-ethoxyethylacetate; dimethyl formamide (DMF); dimethyl sulfoxide (DMSO);tetrahydrofuran (THF); cyclohexanone; chloroform; dichloromethane andcombinations thereof.

The surfactant may be nonionic, anionic or cationic. A nonionicsurfactant is preferably used from the viewpoint of solubility in thephotochromic composition. Preferred examples of the nonionic surfactantinclude sorbitan fatty acid esters, glycerin fatty acid esters,decaglycerin fatty acid esters, propylene glycol⋅pentaerythritol fattyacid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylenesorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters,polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers,polyoxyethylene phytosterol⋅phytostanol, polyoxyethylenepolyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers,polyoxyethylene castor oil⋅hardened castor oil, polyoxyethylenelanoin⋅lanolin alcohol⋅beeswax derivatives, polyoxyethylene alkylamine⋅fatty acid amides, polyoxyethylene alkylphenyl formaldehydecondensates, single-chain polyoxyethylene alkyl ethers andsilicone-based and fluorine-based surfactants.

The surfactants may be used alone or in combination of two or more. Theamount of the surfactant is preferably 0.001 to 5 parts by mass based on100 parts by mass of the polyurethane urea resin (I).

As the antioxidant, radical scavenger, ultraviolet stabilizer andultraviolet absorbent, hindered amine optical stabilizers, hinderedphenol antioxidants, phenol-based radical scavengers, sulfur-basedantioxidants, phosphorus-based antioxidants, triazine-based compoundsbenzotriazole-based compounds and benzophenone-based compounds may bepreferably used. These antioxidants, radical scavengers, ultravioletstabilizers and ultraviolet absorbents may be used in combination of twoor more. To use these additives, the surfactant may be used incombination with the antioxidant, the radical scavenger, the ultravioletstabilizer or the ultraviolet absorbent. The amounts of the antioxidant,the radical scavenger, the ultraviolet stabilizer and the ultravioletabsorbent are each preferably 0.001 to 20 parts by mass based on 100parts by mass of the polyurethane urea resin (I). If these additives areused too much, the adhesion to a polycarbonate resin sheet or film ofthe photochromic composition deteriorates. Therefore, the amounts ofthese additives are each preferably not more than 7 parts by mass, morepreferably not more than 3 parts by mass, most preferably not more than1 part by mass.

<Method of Producing Photochromic Composition>

The photochromic composition used in the laminate of the presentinvention can be produced by mixing together the above polyurethane urearesin (I), the photochromic compound (II) and other components. Theorder of mixing these components is not particularly limited.

For example, these components are melt kneaded together to obtain aphotochromic composition which may be then pelletized or molded into asheet. When an organic solvent is used, a photochromic composition canbe obtained by dissolving these components in the organic solvent.

The photochromic composition obtained as described above can beadvantageously used as a photochromic adhesive, especially aphotochromic adhesive for bonding the polycarbonate optical sheets orfilms of the present invention or a third optical sheet or film whichwill be described hereinafter. The laminate of the present invention canbe easily obtained by bonding the polycarbonate optical sheets or filmsand the third optical sheet or film which will be described hereinafterthrough the adhesive layer composed of the photochromic composition.

The thickness of the adhesive layer composed of the photochromiccomposition is suitably determined according to intended use. Inconsideration of photochromic properties, it is preferably 1 to 100 μm.

The third optical sheet or film may be used in the laminate of thepresent invention besides a pair of opposed polycarbonate optical sheetsor films. A description is subsequently given of the third optical sheetor film used in the present invention.

<Third Optical Sheet or Film>

In the present invention, as the third optical sheet or film, theabove-described polycarbonate optical sheet or film and a cellulosetriacetate film are preferably used.

When the third optical sheet or film in the present invention is formedbetween the polarizing film layer and the photochromic adhesive layer,the adhesion of the laminate of the present invention can be made highand the excellent photochromic properties and polarization properties ofthe laminate of the present invention can be retained. That is, ascompared with a case in which an adhesive layer comprising aphotochromic composition is directly bonded to the surface of apolarizing film (may be referred to as “direct bonding” hereinafter)like technology disclosed by JP-A 2002-062423, high photochromic andpolarization properties can be retained without being affected byheating in the production process.

For example, when a laminate film including a laminate film composed ofa polyvinyl alcohol polarizing film dyed with iodine which is one oftypical polarizing films and an adhesive layer comprising a photochromiccompound disposed on the polarizing film is heated, iodine is diffusedinto the adhesive layer from the polarizing film due to the highsublimability of iodine, whereby the polarization performance of thelaminate film tends to deteriorate.

Further, when a plasticizer is contained in the polyvinyl alcoholpolarizing film to improve moldability in the case of direct bonding,the plasticizer serves as a solvent and the diffusion of thephotochromic compound into the polarizing film from the adhesive layertends to increase by heating. The photochromic compound comes intocontact with iodine to be oxidized by this mechanism, whereby thephotochromic performance of the photochromic compound tends todeteriorate.

In this respect, the inventors of the present invention confirmed thefollowing fact through experiments. That is, it was confirmed that, whenan organic solvent containing 100 parts by mass of a photochromiccompound, specifically6′-(2,3-dihydro-1H-indol-1yl)-1,3-dihydro-3,3-dimethyl-1-propyl-spiro[2H-indol-2,3′-(3H)-naphtho(2,1-b)(1,4)oxazine] (trade name: Reversacol Midnight Grey: manufactured byJames Robinso Ltd.) and 1 part by mass of iodine was heated, the coloroptical density of the organic solvent corresponding to the coloroptical density of the photochromic compound became lower than the coloroptical density of the organic solvent before iodine was added.

Therefore, the laminate of the present invention preferably has thethird optical sheet or film between the polarizing film layer and theadhesive layer composed of the photochromic composition. In this case, aproblem that the above photochromic compound or the dye moves does notoccur.

The thus obtained laminate of the present invention may be used as asunglass lens, sport goggles or polarizing lens such as spectacle lensfor correction. These lenses function as sunglasses as they are coloredswiftly outdoors where they are irradiated with light includingultraviolet light such as sunlight and as ordinary eyeglasses as theyare faded to become transparent indoors where there is no lightirradiation.

In the present invention, when a cellulose triacetate film is used asthe third optical sheet or film, the thickness thereof is preferably 20to 200 μm, more preferably 20 to 100 μm. Since a film having a thicknessof less than 20 μm has low film strength, it is easily broken duringprocessing and a film having a thickness of more than 200 μm is veryexpensive.

An adhesive layer containing no photochromic compound (to be simplyreferred to as “adhesive layer” hereinafter) may also be used in thelaminate of the present invention when the optical sheets or films, thepolarizing film and the adhesive layer composed of the photochromiccomposition are bonded. This adhesive layer does not contain aphotochromic compound unlike the above adhesive layer composed of thephotochromic composition. A description is subsequently given of theadhesive layer used in the present invention.

<Adhesive Layer; Adhesive Layer Containing No Photochromic Compound>

As the above adhesive layer used in the laminate of the presentinvention, any known adhesive layer which is used to bond an opticalsheet or film and a polarizing film may be used. As the adhesive layer,an adhesive layer formed by applying a moisture-curablepolyurethane-based, polyisocyanate-polyester-based two-liquid type,polyisocyanate-polyether-based two-liquid type,polyisocyanate-polyacrylic-based two-liquid type,polyisocyanate-polyurethane elastomer-based two-liquid type,epoxy-based, epoxy-polyurethane-based two-liquid type, polyester-based,acrylic, polyvinyl alcohol-based, polyimide-based, olefin-based, vinylacetate-based or polyurethane urea-based one-liquid type adhesive may beused.

The thickness of the adhesive layer may be suitably determined accordingto intended use. For example, a thickness of 1 to 100 μm suffices forordinary use.

In the present invention, the adhesive layer preferably has such highheat resistance that it can withstand processing temperature at the timeof bending and/or injection molding. Stated more specifically, the aboveheat resistance of the adhesive layer is preferably not lower than 100°C. When the heat resistance of the adhesive layer is not lower than 100°C., the shrinkage of the polarizing film layer by heat at the time ofbending and injection molding can be suppressed with the result that theyield of the optical article can be improved.

The adhesive layer having the above heat resistance is formed by using apolyurethane urea-based one-liquid type adhesive composed of the abovepolyurethane urea resin (I). In this case, from the viewpoint ofimproving the adhesion and heat resistance of the obtained laminate, theadhesive layer formed from the above polyurethane urea resin (I) has aheat resistance of preferably not lower than 100° C., more preferably100 to 190° C., much more preferably 120 to 190° C., particularlypreferably 150 to 190° C. Therefore, when the above polyurethane urearesin (I) is used to form the adhesive layer, the polyurethane urearesin (I) having a heat resistance of not lower than 100° C. ispreferably used by adjusting the constituent components.

To set the heat resistance of the adhesive layer to not lower than 100°C., the polyisocyanate compound having at least two isocyanate groups inthe molecule (III) may be used in combination like the photochromiccomposition. In this case, the adhesive layer contains the abovepolyurethane urea resin (I) and the component (III) but not aphotochromic compound. The adhesive layer formed from a compositioncomprising the polyurethane urea resin (I) having a heat resistance ofnot lower than 80° C. to lower than 120° C. and the component (III) hasimproved adhesion to the polarizing film layer. When the heat resistanceof the adhesive layer composed of the above composition is not lowerthan 100° C., the effect of improving heat resistance and adhesion isobtained. The preferred amount of the component (III) is as describedabove. The preferred component (III) is also as described above. Forexample, the component (III) is preferably at least one polyisocyanatecompound selected from the component (IIIA) and the component (IIIB). Tofurther enhance adhesion, the component (III) is preferably acombination of the above component (IIIA) and the above component(IIIB), the particularly preferred amounts thereof are as describedabove, and the preferred compounds are also as described above.

A description is subsequently given of the laminate of the presentinvention and the production method thereof.

<Laminate and Production Method Thereof>

The laminate of the present invention is a laminate having a laminatestructure formed by bonding together a pair of opposed polycarbonateoptical sheets or films through a polarizing film layer and an adhesivelayer composed of a photochromic composition. This laminate ispreferably one of laminates given below.

(a) The adhesive layer composed of the photochromic composition isformed on the polarizing film simplex, and a polycarbonate optical sheetor film is adhering to the adhesive layer composed of the photochromiccomposition. After the adhesive layer is formed on the polarizing filmside of the obtained laminate sheet, another polycarbonate optical sheetor film is adhering to obtain the laminate of the present invention. Theabove adhesive layer may be formed between the adhesive layer composedof the photochromic composition and the polycarbonate optical sheet orfilm.

(b) A polarizing sheet is prepared by adhering a polycarbonate opticalsheet or film to both sides of the polarizing film layer through theadhesive layer. The adhesive layer composed of the photochromiccomposition is formed on one side of this polarizing sheet and apolycarbonate optical sheet or film is adhering to the adhesive layercomposed of the photochromic composition to obtain the laminate of thepresent invention. The above adhesive layer may be formed between theadhesive layer composed of the photochromic composition and thepolycarbonate optical sheet or film.

(c) A polarizing sheet is prepared by adhering a cellulose triacetatefilm to both sides of the polarizing film layer. The adhesive layercomposed of the photochromic composition is formed on one side of thispolarizing sheet and further a polycarbonate optical sheet or film isadhering to the adhesive layer composed of the photochromic composition.Further, after the adhesive layer is formed on the cellulose triacetatefilm on the other side of the obtained laminate sheet, anotherpolycarbonate optical sheet or film is adhering to obtain the laminateof the present invention. The above adhesive layer may be formed betweenthe adhesive layer composed of the photochromic composition and thepolycarbonate optical sheet or film and further between the adhesivelayer composed of the photochromic composition and the cellulosetriacetate film.

In the laminate of the present invention, by forming the above adhesivelayer between layers, the adhesion of the laminate can be improved andthe laminate of the present invention whose layers are integrated by theadhesive layers can be obtained.

The thickness of the laminate of the present invention is preferably 300to 2,000 μm from the viewpoint of workability in consideration ofoptical distortion and shape at the time of bending into a sphericalshape.

(Preferred Laminate Structure of Laminate)

When the laminate is post-processed before use, for example, when it isbent and when a lens substrate is laminated by injection molding afterbending, the laminate preferably has a laminate structure which isvertically symmetrical with the polarizing film layer as the center. Toobtain a laminate having more excellent performance, a laminate havingthe following laminate structure is preferred.

Stated more specifically, it is a laminate having a laminate structureshown in FIG. 5. Describing in detail, the laminate consists of apolycarbonate optical sheet or film 1, an adhesive layer 8, an adhesivelayer 2 composed of a photochromic composition, a polarizing film layer3, an adhesive layer 9, an adhesive layer 8 and a polycarbonate opticalsheet or film 1′. The adhesive layers 8 and 9 do not contain aphotochromic compound. Not shown, the above third optical sheet or filmmay be formed on both sides of the polarizing film layer 3.

The above adhesive layer 9 may be omitted and only the above adhesivelayer 8 suffices. In consideration of adhesion to the polarizing filmlayer 3 and the adhesion of the finally obtained laminate, the adhesivelayer 9 which differs from the adhesive layer 8 is preferably formed.

Stated more specifically, the adhesive layer 8 is preferably composed ofthe polyurethane urea resin (I) having a heat resistance of preferablynot lower than 100° C., more preferably 100 to 190° C., much morepreferably 120 to 190° C., particularly preferably 150 to 190° C. Thepolyurethane urea resin (I) having this heat resistance can besynthesized by adjusting the amount of each constituent component andthe composition.

Since the adhesive layer 9 is in contact with the polarizing film layer3, it is preferably formed from a composition comprising the abovepolyurethane urea resin (I) having a heat resistance of 80 to 120° C.and the above component (III). The heat resistance of the adhesive layer9 formed from this composition is preferably not lower than 100° C.,more preferably 100 to 190° C., much more preferably 120 to 190° C.,particularly preferably 150 to 190° C.

The adhesive layer 2 composed of the photochromic composition ispreferably formed from a composition comprising the polyurethane urearesin (I) having a heat resistance of 80 to 120° C., the photochromiccompound (II) and the above component (III). The heat resistance of theadhesive layer 2 formed from the photochromic composition is preferablynot lower than 100° C., more preferably 100 to 190° C., much morepreferably 120 to 190° C., particularly preferably 150 to 190° C.

That is, the adhesive layer 8 is preferably formed from a compositioncomprising the polyurethane urea resin (I) having relatively highhardness and high heat resistance. Preferably, the adhesive layer 2 andthe adhesive layer 9 are formed from a composition comprising therelatively soft polyurethane urea resin (I) and the component (III) andchanged into layers having high heat resistance when they are laminated.Since the adhesive layer 2 and the adhesive layer 9 have the aboveconstitutions, the adhesion and bonding property to the polarizing filmlayer 3 of these layers can be further improved. In this case, thepolyurethane urea resin (I) and the component (III) constituting theadhesive layer 2 and the adhesive layer 9 may be the same or differentif they have the same level of heat resistance. However, when theproductivity of the laminate is taken into consideration, they arepreferably of the same type and used in the same amount (the amountcalculated without considering the photochromic compound (II)).

Even when the laminate has a laminate structure shown in FIG. 5, itpreferably has a vertically symmetrical structure with the polarizingfilm layer 3 as the center. Therefore, preferably, the two adhesivelayers 8 above and below the polycarbonate optical sheet or film 1 andthe polycarbonate optical sheet or film 1′ are of the same type and havethe same thickness. Although the adhesive layer 2 composed of thephotochromic composition and the adhesive layer 9 differ from each otheronly in the existence of the photochromic compound, they preferably havethe same composition and the same thickness.

<Optical Article Comprising the Laminate>

An optical article having a polycarbonate layer on the rear side can beobtained from the laminate of the present invention by injection moldingthe same polycarbonate as that of a polycarbonate optical sheet or filmon the rear side on the polycarbonate optical sheet or film on the rearside to integrate them.

As means for integration, there is a method in which the above laminateis set in a mold and a polycarbonate for constituting an opticalsubstrate is injection molded. At this point, the adhesive layercomposed of the photochromic composition is situated on the mold sideand the polarizing film layer is situated on the injection mold side.Before the laminate of the present invention is integrated with theoptical substrate, it can be bent to be formed into a lens-likespherical shape. As means for bending the above laminate, thermalpressing, pressure processing or vacuum suction processing is employed.The temperature at the time of bending is suitably determined accordingto the type of the polycarbonate optical sheet or film used in thelaminate but preferably 100 to 150° C.

EXAMPLES

The following examples are provided for the purpose of furtherillustrating the present invention but are in no way to be taken aslimiting.

Example 1

(1) Production of Polyurethane Urea Resin (U1) (Production of UrethanePrepolymer)

A cooling tube, a thermometer and a nitrogen gas introduction tube wereconnected to a reaction vessel equipped with a max blend blade having adiameter of 135 mm and a baffle plate and having an inner diameter of260 mm, a height of 280 mm and a loading capacity of 10 L. The max blendblade stirred at 100 rpm. 1,770 g of a polycarbonate diol having anumber average molecular weight of 800, 700 g of isophorone diisocyanateand 500 g of toluene were fed to this reaction vessel to carry out areaction in a nitrogen atmosphere at 100° C. for 7 hours so as tosynthesize a urethane prepolymer having an isocyanate group at the end.The end point of the reaction was confirmed by the back titration methodof an isocyanate group.

(Production of Polyurethane Urea Resin (U1))

After the end of the urethane prepolymer reaction, the reaction solutionwas cooled to around 0° C., dissolved in 1,430 g of isopropyl alcoholand 2,670 g of diethyl ketone and kept at a temperature of 0° C.Thereafter, a mixed solution of 171 g of bis-(4-aminocyclohexyl)methaneand 145 g of diethyl ketone as chain extenders was added dropwise within30 minutes to carry out a reaction at 0° C. for 1 hour. Then, 42 g of1,2,2,6,6-pentamethyl-4-aminopiperidine was further added dropwise tocarry out a reaction at 0° C. for 1 hour so as to obtain a diethylketone solution of a polyurethane urea resin (U1). The obtainedpolyurethane urea resin (U1) had a number average molecular weight of19,000, a weight average molecular weight of 41,000, a polydispersity of2.16, a softening point of 105° C. (softening start temperature; about80° C.) and a kinetic viscosity of 15,000 cSt.

The reaction solution at the time of starting the addition ofbis-(4-aminocyclohexyl)methane which is a polyamine compound had aviscosity of 0.06 kg/m·s and a density of 900 kg/m³, the revolution ofthe max blend blade was 100 rpm, the Reynolds number (Re) was 456, andthe mixing time number (n·θ_(M)) was 14 according to the n·θ_(M)−Recurve of the max blend blade. Therefore, the complete mixing time(θ_(M)) was 8 seconds.

<Evaluation Method>

The number average molecular weight, weight average molecular weight,polydispersity, softening point and kinetic viscosity of the abovepolyurethane urea resin (U1) were measured by the following methods.

(Number Average Molecular Weight, Weight Average Molecular Weight,Polydispersity)

The number average molecular weight, the weight average molecular weightand the polydispersity were obtained by carrying out analysis in themethods described in this text.

That is, the number average molecular weight and the weight averagemolecular weight of the above polyurethane urea resin were obtained bymeasuring a 1.0% dimethyl formamide (DMF) solution of the polyurethaneurea resin (U1) sample by using a gel permeation chromatograph (GPC) interms of polyethylene oxide, two Shodex KD-806M columns connected inseries (manufactured by Showa Denko K.K.), a LiBr (10 mmol/L)/DMFsolution as an elute and a RI detector at a flow rate of 1 ml/min andcalculating with the Empower Personal GPC Option GPC analyzing softwareof Nihon Waters K.K. The polydispersity is a weight average molecularweight/number average molecular weight ratio and a value calculated fromnumber average molecular weight and weight average molecular weightobtained by the above method.

(Heat Resistance; Softening Point)

The polyurethane urea resin (U1) was poured into a stainless steelvessel and dried at 40° C. for 10 hours, at 60° C. for 10 hours and at60° C. for 12 hours in a vacuum drier to prepare a test specimen havinga thickness of 1 mm. The softening point of the obtained test specimenwas measured by using a thermomechanical analyzer (TMA120C of SeikoInstruments Inc.) and a needle probe having an end diameter of 0.5 mm ata temperature elevation rate of 10° C./min and a measurement temperaturerange of 30 to 200° C.

(Kinetic Viscosity)

About 10 g of the polyurethane urea resin (U1) solution was charged intoa Canon Fenske viscometer (#600) (made of Shibata Kagaku KK), which wasthen immersed in a thermobath kept at 25° C.±0.1° C. for 15 minutes tomeasure the kinetic viscosity.

(2) Preparation of Photochromic Composition 1

1,000 g of the polyurethane urea resin (U1) solution, 5.7 g of aphotochromic compound (PC1/PC2/PC3=4.0/1.0/0.7 g), 43.2 g of an isomermixture of 4,4′-methylenebis(cyclohexyl isocyanate), 3.6 g ofethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]as an antioxidant and 0.5 g of DOW CORNING TORAY L-7001 as a surfactantwere added, stirred and mixed together at room temperature to obtain aphotochromic composition 1.

PC1: compound represented by the following formula

PC2: compound represented by the following formula

PC3: compound represented by the following formula

(3) Preparation of Polarizing Film

A polyvinyl alcohol film (trade name: VF-PS#7500; manufactured byKuraray Co., Ltd.) raw fabric having a thickness of 75 μm was dyed in amixed solution (dye solution) of 0.04% of iodine and 0.4% of potassiumiodide kept at 30° C. to be dyed while it was stretched to a lengthwhich was 3 times the length of the raw fabric. This film was furtherimmersed in a 3.5% boric acid aqueous solution (stretching bath) andstretched to a length which was 6 times the length of the raw fabric tomanufacture a polarizing film 1 (thickness of 27 μm). The obtainedpolarizing film had a visual transmittance of 42.5% and a polarizationdegree of 99.2%.

(4) Production of Polyurethane Urea Resin (U2)

(Production of Urethane Prepolymer)

A cooling tube, a thermometer and a nitrogen gas introduction tube wereconnected to a reaction vessel equipped with a max blend blade having adiameter of 135 mm and a baffle plate and having an inner diameter of260 mm, a height of 280 mm and a loading capacity of 10 L. The max blendblade stirred at 100 rpm.

800 g of a polycarbonate diol having a number average molecular weightof 1,000, 350 g of isophorone diisocyanate and 250 g of toluene were fedto this reaction vessel to carry out a reaction at 110° C. in a nitrogenatmosphere for 7 hours so as to synthesize a urethane prepolymer havingan isocyanate group at the end. The end point of the reaction wasconfirmed by the back titration method of an isocyanate group.

(Production of Polyurethane Urea Resin (U2))

After the end of the urethane prepolymer reaction, the reaction solutionwas cooled to around 20° C., dissolved in 5,000 g of propyleneglycol-monomethyl ether and kept at a temperature of 20° C. Thereafter,121.5 g of isophorone diamine as a chain extender was added dropwisewithin 30 minutes to carry out a reaction at 20° C. for 1 hour. Then, 9g of n-butylamine was added dropwise to carry out a reaction at 20° C.for 1 hour to obtain a propylene glycol-monomethyl ether solution of apolyurethane urea resin (U2). The obtained polyurethane urea resin (U2)had a number average molecular weight of 49,000, a weight averagemolecular weight of 89,000, a polydispersity of 1.82, a softening pointof 175° C. (softening start temperature; about 155° C.) and a kineticviscosity of 2,500 cSt.

The reaction solution at the time of starting the addition of isophoronediamine which is a polyamine compound had a viscosity of 0.04 kg/m·s anda density of 950 kg/m³, the revolution of the max blend blade was 100rpm, the Reynolds number (Re) was 721, and the mixing time number(n·θ_(M)) was 12 according to the n·θ_(M)−Re curve of the max blendblade. Therefore, the complete mixing time (θ_(M)) was 7 seconds.

(5) Preparation of Adhesive 1 for Adhesive Layers

An adhesive 1 for adhesive layers was obtained by adding 0.7 g of DOWCORNING TORAY L-7001 as a surfactant to 1,000 g of a solution of thepolyurethane urea resin (U2) and stirring and mixing them together atroom temperature.

(6) Production of Laminate

The photochromic composition 1 obtained in (2) was applied to thepolarizing film obtained in (3) by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 3 minutes to obtain apolarizing film having an adhesive layer composed of the photochromiccomposition 1 and having a thickness of 40 μm. Then, a polycarbonatesheet (monoaxially stretched sheet; phase difference of about 4,500 nm)having a thickness of 300 μm was adhering to the adhesive layer composedof the photochromic composition 1.

Further, the adhesive 1 (U2) for adhesive layers obtained in (5) wasapplied to the polarizing film side of the above laminate sheet by usinga coater (manufactured by Tester Sangyo Co., Ltd.) and dried at 80° C.for 5 minutes to form an adhesive layer having a thickness of 3 μm, andthen a polycarbonate optical sheet having a thickness of 300 μm wasadhering to this adhesive layer.

This laminate was left at 40° C. for 1 week to obtain the laminate ofthe present invention having a total thickness of about 670 μm andpolarization properties and photochromic properties.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance at the time ofcolor development of 11.0%, a fading speed of 45 seconds and adurability of 93% as photochromic properties after ultravioletirradiation. The peel strength was 150 N/25 mm at 25° C., 120 N/25 mm ina 70° C. atmosphere and 20 N/25 mm in a 150° C. atmosphere, and theadhesion stability time in a perspiration resistance test was about 400hours (adhesion was retained for 408 hours).

These evaluations were made as follows.

[Visual Transmittance (Before Activated)]

The obtained laminate was used as a specimen and measured for visualtransmittance before the ultraviolet irradiation of the laminate byusing the UV-2550 ultraviolet-visible spectrophotometer of ShimadzuCorporation.

[Polarization Degree (Before Activated)]

Two obtained laminates were used as specimens and measured for parallellight transmittance (Tp) and orthogonal light transmittance (Tc) byusing the UV-2550 ultraviolet-visible spectrophotometer of ShimadzuCorporation to obtain polarization degree (P) from the followingequation.

Polarization degree (P)(%)={(Tp−Tc)/(Tp+Tc)}×100

The above Tp and Tc are Y values obtained by measuring with the 2-degreefield of view (C light source) of JIS Z 8701 and carrying out visibilitycorrection.

[Photochromic Properties]

The obtained laminate was used as a specimen and irradiated with lightfrom the L-2480 (300 W) SHL-100 xenon lamp of Hamamatsu Photonics K.K.through an aeromass filter (manufactured by Corning Co., Ltd.) at 23° C.and a beam strength at 365 nm of 2.4 mW/cm² and at 245 nm of 24 μW/cm²on the surface of the laminate for 120 seconds to develop color so as tomeasure the photochromic properties of the laminate.

Photochromic property; 1) visual transmittance on activated state:visual transmittance measured with the spectrophotometer (MCPD1000instantaneous multi-channel photodetector) of Otsuka Electronics Co.,Ltd. after 120 seconds of exposure to the above light

Photochromic property; 2) fading speed [t½(sec)]: The maximum absorptionwavelength after activated state was first obtained by thespectrophotometer (MCPD1000 instantaneous multi-channel photodetector)of Otsuka Electronics Co., Ltd. Then, the difference [ε (120)−ε (0)]between absorbance ε (120) after 120 seconds of irradiation at the abovemaximum absorption wavelength and absorbance ε (0) without irradiationat the maximum absorption wavelength was obtained and then time (fadingspeed) required until the absorbance at the above maximum wavelength ofthe specimen was reduced to ½ of [ε (120)−ε (0)] was obtained. It can besaid that as this time becomes shorter, the photochromic propertiesbecome more excellent.

Photochromic property; 3) durability (%)=[(A96/A0)×100]: The followingaccelerated deterioration test was carried out to evaluate colordevelopment durability by irradiation. That is, the obtained laminatewas subjected to accelerated deterioration for 96 hours with the X25xenon weather meter of Suga Test Instruments Co., Ltd. Thereafter, theabove color optical density was evaluated before and after the test tomeasure color optical density (A0) before the test and color opticaldensity (A96) after the test, and the value [(A96/A0)×100] was taken asa residual rate (%) which is an index for color development durability.As the residual rate becomes higher, durability becomes higher.

[Peel Strength]

The obtained laminate was formed into a test specimen having a bondedpart measuring 25×100 mm which was set in a tester (AGS-500NX autographof Shimadzu Corporation) equipped with a thermostat which can set a testambient temperature to carry out a tensile test at a cross head speed of100 mm/min so as to measure the following peel strengths 1) to 3).

Peel strength; 1) Peel strength at 25° C. was measured as describedabove after the specimen having the above size was left in a thermostatset to 25° C. for 10 minutes.

Peel strength: 2) Peel strength in a 70° C. atmosphere was measured asdescribed above after the specimen having the above size was heated in athermostat set to 70° C. for 10 minutes.

Peel strength; 3) Peel strength in a 150° C. atmosphere was measured asdescribed above after the specimen having the above size was heated in athermostat set to 150° C. for 10 minutes.

[Perspiration Resistance Test]

The obtained laminate was cut into a circular shape having a diameter of50 mm, and the periphery of this test specimen was clamped with astainless steel ring jig. Separately, artificial perspiration (distilledwater containing 10% of common salt and 5% of lactic acid) contained ina plastic vessel with a lid was prepared, and the above test specimenwas immersed in this artificial perspiration. The plastic vesselcontaining this test specimen and artificial perspiration was kept at70° C. to visually check the existence of a peeled end of the testspecimen every 24 hours. The numerical value of the evaluation result isa time during which the test specimen had stable adhesion (time rightbefore peeling occurs).

Example 2

The laminate obtained in Example 1 was thermally bent into a sphericalshape in such a manner that the adhesive layer composed of thephotochromic composition 1 became the convex side and the polarizingfilm layer became the concave side. Thermal bending was carried out bypreparing a concave mold having a suction port capable of vacuum suctionwith the mold as the center, placing the laminate having a diameter of80 mm which had been diecut such that the adhesive layer composed of thephotochromic composition 1 was situated on the mold side, and thenvacuum sucking it at 130° C. for 5 minutes. Thereby, a sphericallaminate having the adhesive layer composed of the photochromiccomposition 1 on the convex side and the polarizing film layer on theconcave side was obtained.

Then, the obtained spherical laminate was set in the concave mold of aninjection molding machine and heated at 100° C. A polycarbonate resinpellet (Panlite of Teijin Chemicals Ltd.) which had been preheated at120° C. for 5 hours was filled into the injection molding machine andthermally molten at 300° C. and 60 rpm to be injected onto the rear side(polarizing film layer side) of the laminate at an injection pressure of14,000 N/cm², thereby producing a plastic lens (optical article)integrated with the polycarbonate resin. The obtained plastic lens had avisual transmittance of 40.5%, a polarization degree of 99.1%, and avisual transmittance on activated state of 11.0%, a fading speed of 45seconds and durability of 93% as photochromic properties afterultraviolet irradiation. The adhesion stability time in a perspirationresistance test was about 1,000 hours (adhesion was retained for 1,008hours). The bending workability was A. The evaluation of bendingworkability was carried out as follows.

[Bending Workability]

After the above bending, a laminate which could be bent into a desiredshape was visually evaluated as A, a laminate which was slightlydistorted was visually evaluated as B, and a laminate which was so muchdistorted that it was hardly set in the mold of an injection moldingmachine was visually evaluated as C.

Example 3

The photochromic composition 1 obtained in (2) was applied to thepolarizing film obtained in (3) by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 3 minutes to obtain apolarizing film having an adhesive layer composed of the photochromiccomposition 1 and having a thickness of 40 μm. Then, a polycarbonatesheet (monoaxially stretched sheet: phase difference of about 4,500 nm)having a thickness of 300 μm was adhering to this adhesive layercomposed of the photochromic composition 1.

Further, an acrylic adhesive (Saibinol AT-245 of Saiden ChemicalIndustry Co., Ltd.) was applied to the polarizing film of the abovelaminate sheet by using a coater (manufactured by Tester Sangyo Co.,Ltd.) and dried at 80° C. for 5 minutes to form an adhesive layer havinga thickness of 10 μm, and then a polycarbonate optical sheet having athickness of 300 μm was adhering to this adhesive layer.

This laminate was left at 40° C. for 1 week to obtain the laminate ofthe present invention having a total thickness of about 677 μm andpolarization properties and photochromic properties.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 120 N/25 mm at room temperature, 90 N/25 mm in a 70° C. atmosphereand 10 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 200 hours (adhesion wasretained for 216 hours).

Example 4

The laminate obtained in Example 3 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.6%, a polarization degreeof 99.1%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 500 hours (adhesion wasretained for 504 hours). The bending workability was B.

Example 5

The photochromic composition 1 obtained in (2) was applied to thepolarizing film obtained in (3) by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 3 minutes to obtain apolarizing film having an adhesive layer composed of the photochromiccomposition 1 and having a thickness of 40 μm. Then, a polycarbonatesheet (monoaxially stretched sheet: phase difference of about 4,500 nm)having a thickness of 300 μm was adhering to this adhesive layercomposed of the photochromic composition 1.

Further, an olefin-based adhesive (Ricon 142 of Tomoe Engineering Co.,Ltd.) was applied to the polarizing film of the above laminate sheet byusing a coater (manufactured by Tester Sangyo Co., Ltd.) and dried at80° C. for 5 minutes to form an adhesive layer having a thickness of 10μm, and then a polycarbonate optical sheet having a thickness of 300 μmwas attached to this adhesive layer.

This laminate was left at 40° C. for 1 week to obtain the laminate ofthe present invention having a total thickness of about 677 μm andpolarization properties and photochromic properties.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 120 N/25 mm at room temperature, 80 N/25 mm in a 70° C. atmosphereand 10 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 200 hours (adhesion wasretained for 216 hours).

Example 6

The laminate obtained in Example 5 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.6%, a polarization degreeof 99.1%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration test was about 400 hours (adhesion was retained for 408hours). The bending workability was B.

Example 7

The photochromic composition 1 obtained in (2) was applied to thepolarizing film obtained in (3) by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 3 minutes to obtain apolarizing film having an adhesive layer composed of the photochromiccomposition 1 and having a thickness of 40 μm. Then, a polycarbonatesheet (monoaxially stretched sheet: phase difference of about 4,500 nm)having a thickness of 300 μm was adhering to this adhesive layercomposed of the photochromic composition 1.

Further, a coating solution prepared by mixing together amoisture-curable urethane adhesive (Takenate of Mitsui Takeda Chemicals,Inc.) and a triisocyanate-based curing agent was applied to thepolarizing film of the above laminate sheet by using a coater(manufactured by Tester Sangyo Co., Ltd.) and dried at 80° C. for 5minutes to form an adhesive layer having a thickness of 10 μm, and then,a polycarbonate optical sheet having a thickness of 300 μm was adheringto this adhesive layer.

This laminate was left at 40° C. for 1 week to obtain the laminate ofthe present invention having a total thickness of about 677 μm andpolarization properties and photochromic properties.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 160 N/25 mm at room temperature, 120 N/25 mm in a 70° C. atmosphereand 20 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 450 hours (adhesion wasretained for 456 hours).

Example 8

The laminate obtained in Example 7 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.6%, a polarization degreeof 99.1%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 1,000 hours (adhesion wasretained for 1,008 hours). The bending workability was B.

Example 9

The photochromic composition 1 obtained in (2) was applied to thepolarizing film obtained in (3) by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 3 minutes to obtain apolarizing film having an adhesive layer composed of the photochromiccomposition 1 and having a thickness of 40 μm. Then, a polycarbonatesheet (monoaxially stretched sheet: phase difference of about 4,500 nm)having a thickness of 300 μm was attached to this adhesive layercomposed of the photochromic composition 1.

Further, a polyvinyl alcohol-based adhesive (Gohsenol of The NipponSynthetic Chemical Industry Co., Ltd.) was applied to the polarizingfilm of the above laminate sheet by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 5 minutes to form anadhesive layer having a thickness of 10 μm, and then a polycarbonateoptical sheet having a thickness of 300 μm was attached to this adhesivelayer.

This laminate was left at 40° C. for 1 week to obtain the laminate ofthe present invention having a total thickness of about 677 μm andpolarization properties and photochromic properties.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 130 N/25 mm at room temperature, 100 N/25 mm in a 70° C. atmosphereand 15 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 350 hours (adhesion wasretained for 360 hours).

Example 10

The laminate obtained in Example 7 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.6%, a polarization degreeof 99.1%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 800 hours (adhesion wasretained for 816 hours). The bending workability was B.

Example 11

The adhesive 1 for adhesive layers obtained in (5) was applied to thepolarizing film obtained in (3) by using a coater (manufactured byTester Sangyo Co., Ltd.) and dried at 80° C. for 3 minutes to obtain apolarizing film having an adhesive layer with a thickness of 3 μm. Apolycarbonate sheet (monoaxially stretched sheet: phase difference ofabout 4,500 nm) having a thickness of 150 μm was attached to thisadhesive layer.

Further, the adhesive 1 for adhesive layers obtained in (5) was appliedto the other side of the polarizing film by using a coater (manufacturedby Tester Sangyo Co., Ltd.) and dried at 80° C. for 5 minutes to form anadhesive layer having a thickness of 3 μm, and a polycarbonate sheethaving a thickness of 300 μm was attached to this adhesive layer toobtain a polarizing sheet sandwiched between two polycarbonate sheets.

The photochromic composition 1 obtained in (2) was applied to thepolycarbonate sheet (monoaxially stretched sheet; phase difference ofabout 4,500 nm) having a thickness of 150 μm of the polarizing sheet byusing a coater (manufactured by Tester Sangyo Co., Ltd.) and dried at80° C. for 3 minutes to obtain a polarizing sheet having an adhesivelayer composed of the photochromic composition 1 and having a thicknessof 40 μm. Then, a polycarbonate sheet (monoaxially stretched sheet:phase difference of about 4,500 nm) having a thickness of 150 μm wasattached to this adhesive layer composed of the photochromic composition1.

This laminate was left at 40° C. for 1 week to obtain a laminate havinga total thickness of about 673 μm and polarization properties andphotochromic properties.

The obtained laminate had a visual transmittance of 41.3%, apolarization degree of 99.2%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 140 N/25 mm at room temperature, 110 N/25 mm in a 70° C. atmosphereand 20 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 400 hours (adhesion wasretained for 408 hours).

Example 12

The laminate obtained in Example 11 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.6%, a polarization degreeof 99.1%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 1,000 hours (adhesion wasretained for 1,008 hours). The bending workability was A.

Example 13

A laminate having the same constitution as that of Example 3 wasobtained except that an adhesive layer was formed by applying theadhesive 1 for adhesive layers obtained in (5) to both sides of theadhesive layer composed of the photochromic composition 1 in thelaminate obtained in Example 11. The total thickness of this laminatewas about 680 μm.

The obtained laminate had a visual transmittance of 41.5%, apolarization degree of 99.0%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 180 N/25 mm at room temperature, 125 N/25 mm in a 70° C. atmosphereand 30 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 800 hours (adhesion wasretained for 816 hours).

Example 14

The laminate obtained in Example 13 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.8%, a polarization degreeof 99.0%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 1,400 hours (adhesion wasretained for 1, 416 hours). The bending workability was A.

Example 15

A laminate having the same constitution as that of Example 13 wasobtained except that an adhesive layer was formed by applying a coatingsolution prepared by mixing together a moisture-curable urethaneadhesive (Takenate of Mitsui Takeda Chemicals, Inc.) and atriisocyanate-based curing agent to both sides of the adhesive layercomposed of the photochromic composition 1 in the laminate obtained inExample 11. The total thickness of this laminate was about 680 μm.

The obtained laminate had a visual transmittance of 41.5%, apolarization degree of 99.0%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 170 N/25 mm at room temperature, 125 N/25 mm in a 70° C. atmosphereand 30 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 700 hours (adhesion wasretained for 720 hours).

Example 16

The laminate obtained in Example 15 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.8%, a polarization degreeof 99.0%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 1,300 hours (adhesion wasretained for 1,320 hours). The bending workability was B.

Example 17

A laminate having the same constitution as that of Example 13 wasobtained except that an adhesive layer was formed by applying apolyvinyl alcohol-based adhesive (Gohsenol of The Nippon SyntheticChemical Industry, Co., Ltd.) to one side of the adhesive layer composedof the photochromic composition 1 and applying an acrylic adhesive(Saibinol AT-245 of Saiden Chemical Industry Co., Ltd.) to the otherside of the adhesive layer composed of the photochromic composition 1 inthe laminate obtained in Example 11. The total thickness of thislaminate was about 680

The obtained laminate had a visual transmittance of 41.5%, apolarization degree of 99.0%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 130 N/25 mm at room temperature, 110 N/25 mm in a 70° C. atmosphereand 20 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 500 hours (adhesion wasretained for 504 hours).

Example 18

The laminate obtained in Example 17 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.8%, a polarization degreeof 99.0%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 1,100 hours (adhesion wasretained for 1,104 hours). The bending workability was B.

Example 19

A polarizing sheet (Sumikaran SQ-1852A of Sumitomo Chemical Co., Ltd.)having a thickness of 180 μm and a visual transmittance of 43.7% wasused as a polarizing film. This polarizing film was prepared by bondinga cellulose triacetate film having a thickness of 80 μm to both sides ofa polarizing film having a thickness of 20 μm and composed of polyvinylalcohol having a polarization degree of 99.9% by using a iodine-baseddye.

The adhesive 1 for adhesive layers obtained in (5) was applied to thepolarizing sheet described in (3) by using a coater (Tester Sangyo Co.,Ltd.) and dried at 80° C. for 5 minutes to obtain a polarizing sheethaving an adhesive layer with a thickness of 3 μm. A polycarbonate sheethaving a thickness of 300 μm was attached to this adhesive layer.

Further, the photochromic composition 1 obtained in (2) was applied tothe surface of the cellulose triacetate film on the other side of thepolarizing sheet by using a coater (manufactured by Tester Sangyo Co.,Ltd.) and dried at 80° C. for 3 minutes to form an adhesive layercomposed of the photochromic composition 1 and having a thickness of 40μm, and then a polycarbonate sheet having a thickness of 150 μm(monoaxially stretched sheet; phase difference of about 4,500 nm) wasattached to this adhesive layer.

This laminate was left at 40° C. for 1 week to obtain a laminate havinga total thickness of about 673 μm and polarization properties andphotochromic properties.

The obtained laminate had a visual transmittance of 43.3%, apolarization degree of 99.9%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 140 N/25 mm at room temperature, 110 N/25 mm in a 70° C. atmosphereand 20 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 400 hours (adhesion wasretained for 408 hours).

Example 20

The laminate obtained in Example 19 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 43.2%, a polarization degreeof 99.9%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 900 hours (adhesion wasretained for 912 hours). The bending workability was A.

Example 21

A laminate having the same constitution as that of Example 19 wasobtained except that an adhesive layer was formed by applying theadhesive 1 for adhesive layers obtained in (5) to both sides of theadhesive layer composed of the photochromic composition 1 in thelaminate obtained in Example 19. The total thickness of this laminatewas about 686 μm.

The obtained laminate had a visual transmittance of 43.3%, apolarization degree of 99.9%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 93% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 180 N/25 mm at room temperature, 125 N/25 mm in a 70° C. atmosphereand 30 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 800 hours (adhesion wasretained for 816 hours).

Example 22

The laminate obtained in Example 21 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 43.2%, a polarization degreeof 99.9%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 93% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 1,400 hours (adhesion wasretained for 1, 416 hours). The bending workability was A.

Example 23 Production of Polyurethane Urea Resin (U3)

A polyurethane urea resin for the adhesive layer composed of aphotochromic composition was produced in the same manner as in (1) aboveexcept that the revolution of the max blend blade at the start of addingdropwise bis-(4-aminocyclohexyl) methane which is a polyamine compoundwas changed to 40 rpm. The obtained polyurethane urea resin (U3) had anumber average molecular weight of 21,000, a weight average molecularweight of 54,000, a polydispersity of 2.57, a softening point of 100° C.(softening start temperature; about 50° C.) and a kinetic viscosity of5,5000 cSt.

Since the Reynolds number (Re) became 192 by changing the revolution ofthe max blend blade at the start of adding dropwisebis-(4-aminocyclohexyl)methane which is a polyamine compound to 40 rpmand the mixing time number (n·θ_(M)) was 25 according to the n·θ_(M)−Recurve of the max blend blade, the complete mixing time (θ_(M)) was 38seconds.

Then, a photochromic composition 2 was obtained in the same manner as in(2) except that a solution of the polyurethane urea resin (U3) was used.

Further, a laminate was obtained in the same manner as in Example 1except that the photochromic composition 2 was used in place of thephotochromic composition 1. This laminate had a total thickness of about670 μm and polarization properties and photochromic properties.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 91% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 140 N/25 mm at room temperature, 80 N/25 mm in a 70° C. atmosphereand 20 N/25 mm in a 150° C. atmosphere, and the adhesion stability timein a perspiration resistance test was about 100 hours (adhesion wasretained for 96 hours).

Example 24

The laminate obtained in Example 23 was thermally bent and injectionmolded in the same manner as in Example 2 to produce a plastic lens(optical article) integrated with a polycarbonate resin. The obtainedplastic lens had a visual transmittance of 40.5%, a polarization degreeof 99.1%, and a visual transmittance on activated state of 11.0%, afading speed of 45 seconds and a durability of 91% as photochromicproperties after ultraviolet irradiation. The adhesion stability time ina perspiration resistance test was about 300 hours (adhesion wasretained for 312 hours). The bending workability was B.

Example 25 (Laminate Shown in FIG. 5)

The adhesive 1 for adhesive layers obtained in (5) was applied to apolycarbonate sheet having a thickness of 300 μm (monoaxially stretchedsheet; phase difference of about 4,500 nm) by using a coater (TesterSangyo Co., Ltd.) and dried at 80° C. for 5 minutes to form an adhesivelayer having a thickness of 5 μm (adhesive layer 8 shown in FIG. 5).Then, the photochromic composition 1 obtained in (2) was applied to aPET (polyethylene terephthalate) film (Purex film having a siliconcoating film, manufactured by Teijin DuPont Films Japan Limited) anddried at 110° C. for 10 minutes to forma photochromic layer having athickness of 40 μm which was then attached to the above adhesive layer(adhesive layer 8 shown in FIG. 5).

Separately, the adhesive 1 for adhesive layers obtained in (5) wasapplied to a polycarbonate sheet having a thickness of 300 μm by using acoater (manufactured by Tester Sangyo Co., Ltd.) and dried at 80° C. for5 minutes to form an adhesive layer having a thickness of 5 μm (adhesivelayer 8 shown in FIG. 5). Then, an adhesive 2 for adhesive layersobtained in (7) below was applied to a PET (polyethylene terephthalate)film (Purex film having a silicon coating film, manufactured by TeijinDuPont Films Japan Limited) and dried at 110° C. for 10 minutes to forma layer composed of the adhesive 2 for adhesive layers and having athickness of 40 μm which was then attached to the adhesive layer(adhesive layer 8 shown in FIG. 5) formed on the above polycarbonatesheet.

The polarizing film 1 of (3) was sandwiched between the above twodifferent sheets while the PET films were peeled off from the abovesheets. The obtained laminate was left at 40° C. under vacuum for 24hours, heated at 90° C. for 60 minutes, humidified at 60° C. and 100 RHfor 24 hours and finally left to stand at 40° C. under vacuum for 24hours to obtain a laminate having a laminate structure shown in FIG. 5,polarization properties and photochromic properties and a totalthickness of 710 μm. The layer configuration of this laminate hadheat-resistant symmetry.

(7) Preparation of Adhesive 2 for Adhesive Layers

1,000 g of a solution of the polyurethane urea resin (U1), 43.2 g of anisomer mixture of 4,4′-methylenebis(cyclohexyl isocyanate) and 0.5 g ofDOW CORNING TORAY L-7001 as a surfactant were added, stirred and mixedtogether at room temperature to obtain an adhesive 2 for adhesivelayers. This adhesive 2 for adhesive layers had the same composition asthat of the above photochromic composition 1 except that this did notcontain a photochromic compound.

The evaluation of the obtained laminate was carried out in the samemanner as in Example 1

Example 26

The laminate obtained in Example 25 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 5.

Example 27

The same operation as that of Example 1 was made on the laminateobtained in Example 1 except that a photochromic composition 3 below wasused in place of the photochromic composition 1 to obtain a laminatehaving the same constitution as that of Example 1 and evaluate it in thesame manner as in Example 1. The total thickness of this laminate wasabout 670 μm.

(8) Preparation of Photochromic Composition 3

1,000 g of a solution of the photochromic urea resin (U1), 5.7 g of aphotochromic compound (PC1/PC2/PC3=4.0/1.0/0.7 g), 3.6 g ofethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]as an antioxidant and 0.5 g of DOW CORNING TORAY L-7001 as a surfactantwere added, stirred and mixed together at room temperature to obtain aphotochromic composition 3.

Example 28

The laminate obtained in Example 27 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2.

Example 29

The same operation as that of Example 25 was made on the laminateobtained in Example 25 except that the photochromic composition 3 wasused in place of the photochromic composition 1 to obtain a laminatehaving the same constitution as that of Example 25 and evaluate it inthe same manner as in Example 25. The total thickness of this laminatewas about 710 μm.

Example 30

The laminate obtained in Example 29 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2.

Example 31

The same operation as that of Example 25 was made on the laminateobtained in Example 25 except that the thickness of the adhesive layerobtained from the adhesive 2 for adhesive layers was changed to 5 μm toobtain a laminate having the same constitution as that of Example 25 andevaluate it in the same manner as in Example 25. The total thickness ofthis laminate was about 675 μm.

Example 32

The laminate obtained in Example 31 was used to manufacture a plasticlens (optical article) and evaluate in the same manner as in Example 2.

Example 33

A laminate was produced in the same manner as in Example 25 except thata photochromic composition 5 shown in Table 2 was used in place of thephotochromic composition 1 and an adhesive 3 for adhesive layers shownin Table 3 was used in place of the adhesive 2 for adhesive layers. Theevaluation results are shown in Table 5.

The photochromic composition 5 was prepared in the same manner as in (2)except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 2.

The adhesive 3 for adhesive layers was prepared in the same manner as in(7) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 3.This adhesive 3 for adhesive layers had the same composition as that ofthe above photochromic composition 5 except that it did not contain aphotochromic compound.

Example 34

The laminate obtained in Example 33 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 6.

Example 35

A laminate was produced in the same manner as in Example 25 except thata photochromic composition 6 shown in Table 2 was used in place of thephotochromic composition 1 and an adhesive 4 for adhesive layers shownin Table 3 was used in place of the adhesive 2 for adhesive layers. Theevaluation results are shown in Table 5.

The photochromic composition 6 was prepared in the same manner as in (2)except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 2.

The adhesive 4 for adhesive layers was prepared in the same manner as in(7) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 3.This adhesive 4 for adhesive layers had the same composition as theabove photochromic composition 6 except that it did not contain aphotochromic compound.

Example 36

The laminate obtained in Example 35 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 6.

Example 37

A laminate was produced in the same manner as in Example 25 except thata photochromic composition 7 shown in Table 2 was used in place of thephotochromic composition 1 and an adhesive 5 for adhesive layers shownin Table 3 was used in place of the adhesive 2 for adhesive layers. Theevaluation results are shown in Table 5.

The photochromic composition 7 was prepared in the same manner as in (2)except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 2.

The adhesive 5 for adhesive layers was prepared in the same manner as in(7) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 3.This adhesive 5 for adhesive layers had the same composition as theabove photochromic composition 7 except that it did not contain aphotochromic compound.

Example 38

The laminate obtained in Example 37 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 6.

Example 39

A laminate was produced in the same manner as in Example 25 except thata photochromic composition 8 shown in Table 2 was used in place of thephotochromic composition 1 and an adhesive 6 for adhesive layers shownin Table 3 was used in place of the adhesive 2 for adhesive layers. Theevaluation results are shown in Table 5.

The photochromic composition 8 was prepared in the same manner as in (2)except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 2.

The adhesive 6 for adhesive layers was prepared in the same manner as in(7) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and a burette compound of hexamethylene diisocyanate(IIIB) were used as the component (III) in a ratio shown in Table 3.This adhesive 6 for adhesive layers had the same composition as theabove photochromic composition 8 except that it did not contain aphotochromic compound.

Example 40

The laminate obtained in Example 39 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 6.

Example 41

A laminate was produced in the same manner as in Example 25 except thata photochromic composition 9 shown in Table 2 was used in place of thephotochromic composition 1 and an adhesive 7 for adhesive layers shownin Table 3 was used in place of the adhesive 2 for adhesive layers. Theevaluation results are shown in Table 5.

The photochromic composition 9 was prepared in the same manner as in (2)except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and an isocyanurate compound of hexamethylenediisocyanate (IIIB) were used as the component (III) in a ratio shown inTable 2.

The adhesive 7 for adhesive layers was prepared in the same manner as in(7) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and an isocyanurate compound of hexamethylenediisocyanate (IIIB) were used as the component (III) in a ratio shown inTable 3. This adhesive 7 for adhesive layers had the same composition asthe above photochromic composition 9 except that it did not contain aphotochromic compound.

Example 42

The laminate obtained in Example 41 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 6.

Example 43

A laminate was produced in the same manner as in Example 25 except thata photochromic composition 10 shown in Table 2 was used in place of thephotochromic composition 1 and an adhesive 8 for adhesive layers shownin Table 3 was used in place of the adhesive 2 for adhesive layers. Theevaluation results are shown in Table 5.

The photochromic composition 10 was prepared in the same manner as in(2) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and an isocyanurate compound of hexamethylenediisocyanate (IIIB) were used as the component (III) in a ratio shown inTable 2.

The adhesive 8 for adhesive layers was prepared in the same manner as in(7) except that an isomer mixture of 4,4′-methylenebis(cyclohexylisocyanate) (IIIA) and an isocyanurate compound of hexamethylenediisocyanate (IIIB) were used as the component (III) in a ratio shown inTable 3. This adhesive 8 for adhesive layers had the same composition asthe above photochromic composition 10 except that it did not contain aphotochromic compound.

Example 44

The laminate obtained in Example 43 was used to manufacture a plasticlens (optical article) and evaluate it in the same manner as in Example2. The evaluation results are shown in Table 6.

Comparative Example 1 (1′) Production of Polyurethane Urea Resin forAdhesive Layer Composed of Photochromic Composition

A polyurethane resin (PI) having an isocyanate group at the end of themolecular chain and a polyurethane resin (PII) having a hydroxyl groupat the end of the molecular chain were synthesized by the followingmethods.

(Synthesis of Polyurethane Resin (PI))

100 g of polycaprolactone polyol having a number average molecularweight of 1,000 (Placcel of Daicel Chemical Industries Ltd.) and 39.5 gof 4,4′-methylenebis(cyclohexyl isocyanate) were fed to a three-neckedflask having a stirring blade, a cooling tube, a thermometer and anitrogen gas introduction tube to carry out a reaction at 90° C. in anitrogen atmosphere for 6 hours so as to obtain a prepolymer having anisocyanate group at the end (polyurethane resin (PI)). The molecularweight of the obtained prepolymer (polyurethane resin (PI)) was 2,500(theoretical value; 2,800) in terms of polyoxyethylene.

(Synthesis of Polyurethane Resin (PII))

100 g of polycaprolactone polyol having a number average molecularweight of 1,000 (Placcel of Daicel Chemical Industries Ltd.) and 61.3 gof hydrogenated diphenymethane diisocyanate were fed to a three-neckedflask having a stirring blade, a cooling tube, a thermometer and anitrogen gas introduction tube to carry out a reaction at 90° C. in anitrogen atmosphere for 6 hours so as to obtain a prepolymer having anisocyanate group at the end. After 200 ml of toluene was added, 12.7 gof 1,4-butanediol was added dropwise in a nitrogen atmosphere to carryout a reaction at 90° C. for 24 hours after the end of addition so as tosynthesize a polyurethane resin having a hydroxyl group at the end ofthe molecular chain (PII). The molecular weight of the obtainedpolyurethane resin (PII) was 20,000 (theoretical value; 18,000) in termsof polyoxyethylene.

(2′) Preparation of Photochromic Composition

175 g of the polyurethane resin (PI) obtained as described above, 376 gof a polyurethane resin (PII) solution, 5.7 g of a photochromic compound(PC1/PC2/PC3=4.0/1.0/0.7 g), 3.6 g ofethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]as an antioxidant and 0.5 g of DOW CORNING TORAY L-7001 as a surfactantwere added, stirred and mixed together at room temperature to obtain aphotochromic composition.

(3) The preparation of a polarizing film, (4) the production of apolyurethane urea resin for adhesive layer, (5) the preparation of anadhesive for adhesive layer, and (6) the production of a laminate werecarried out completely in the same manner as in Example 1.

The obtained laminate had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 60% asphotochromic properties after ultraviolet irradiation. The peel strengthwas 80 N/25 mm initially, 50 N/25 mm in a 70° C. atmosphere and 5 N/25mm in a 150° C. atmosphere, and the adhesion stability time in aperspiration resistance test was about 24 hours.

Comparative Example 2

The laminate obtained in Comparative Example 1 was thermally bent andinjection molded in the same manner as in Example 2 to produce a plasticlens (optical article) integrated with a polycarbonate resin. Theobtained plastic lens had a visual transmittance of 41.0%, apolarization degree of 99.1%, and a visual transmittance on activatedstate of 11.0%, a fading speed of 45 seconds and a durability of 60% asphotochromic properties after ultraviolet irradiation. The adhesionstability time in a perspiration resistance test was about 48 hours.

The physical properties of the resins used in the adhesive layers of thepresent invention are shown in Tables 1, 2 and 3, and the laminateconfigurations of the laminates of the present invention are shown inTable 4. The evaluation results of the laminates of the presentinvention and the evaluation results of the plastic lenses are shown inTables 5 and 6. As for the softening points of the photochromiccompositions and the adhesives for adhesive layers, the softening pointsof adhesive layers composed of photochromic compositions obtained bycarrying out the same processing as in Examples and Comparative Examplesand adhesive layers composed of the adhesives for adhesive layers areshown in Tables 2 and 3.

TABLE 1 number weight average average softening molecular molecularsoftening start kinetic Resin weight weight polydispersity pointtemperature viscosity component (Mn) (Mw) (Mw/Mn) (° C.) (° C.) (cSt)Polyurethane 19,000 41,000 2.16 105 About 80 15,000 urea resin (U1)Polyurethane 49,000 89,000 1.82 175  About 155 2,500 urea resin (U2)Polyurethane 21,000 54,000 2.57 100 About 50 55,000 urea resin (U3)Polyurethane — 2,500 — — — — resin (PI) Polyurethane — 20,000 — — — —resin (PII)

TABLE 2 amount of polyisocyanate softening Resin as polyisocyanatecompound as compound as component point component (I) component (III)(III) *2 (° C.) *1 Photochromic polyurethane (IIIA) isomer mixture of 12170 composition 1 urea resin 4,4′-methylenebis(cyclohexyl (U1)isocyanate) Photochromic polyurethane (IIIA) isomer mixture of 12 160composition 2 urea resin 4,4′-methylenebis(cyclohexyl (U3) isocyanate)Photochromic polyurethane — — 105 composition 3 urea resin (U1)Photochromic polyurethane — — 80 composition 4 resin (PI) polyurethaneresin (PII) Photochromic polyurethane (IIIA) isomer mixture of(IIIA)12.5/(IIIB)2.5 160 composition 5 urea resin4,4′-methylenebis(cyclohexyl ((IIIA)100/(IIIB)20) (U1)isocyanate)/(IIIB) burette compound of hexamethylene diisocyanatePhotochromic polyurethane (IIIA) isomer mixture of (IIIA)10/(IIIB)5 150composition 6 urea resin 4,4′-methylenebis(cyclohexyl((IIIA)100/(IIIB)50) (U1) isocyanate)/(IIIB) burette compound ofhexamethylene diisocyanate Photochromic polyurethane (IIIA) isomermixture of  (IIIA)8.5/(IIIB)6.5 140 composition 7 urea resin4,4′-methylenebis(cyclohexyl ((IIIA)100/(IIIB)76) (U1)isocyanate)/(IIIB) burette compound of hexamethylene diisocyanatePhotochromic polyurethane (IIIA) isomer mixture of  (IIIA)7.5/(IIIB)7.5135 composition 8 urea resin 4,4′-methylenebis(cyclohexyl ((IIIA)100/(IIIB)100) (U1) isocyanate)/(IIIB) burette compound ofhexamethylene diisocyanate Photochromic polyurethane (IIIA) isomermixture of  (IIIA)6.5/(IIIB)8.5 120 composition 9 urea resin4,4′-methylenebis(cyclohexyl  ((IIIA)100/(IIIB)131) (U1)isocyanate)/(IIIB) isocyanurate compound of hexamethylene diisocyanatePhotochromic polyurethane (IIIA) isomer mixture of (IIIA)10/(IIIB)5 150composition 10 urea resin 4,4′-methylenebis(cyclohexyl((IIIA)100/(IIIB)50) (U1) isocyanate)/(IIIB) isocyanurate compound ofhexamethylene diisocyanate *1; This softening point is the softeningpoint of an adhesive layer. *2; amount based on 100 parts by mass of thecomponent (I) Figures within parentheses show the amount of thecomponent (IIIB) based on 100 parts by mass of the component (IIIA).

TABLE 3 amount of polyisocyanate softening Resin as polyisocyanatecompound as compound as component point component (I) component (III)(III) *2 (° C.) *1 adhesive 1 polyurethane — — 175 for adhesive urearesin layer (U2) adhesive 2 polyurethane (IIIA) isomer mixture of 12 170for adhesive urea resin 4,4′-methylenebis(cyclohexyl layer (U1)isocyanate) adhesive 3 polyurethane (IIIA) isomer mixture of(IIIA)12.5/(IIIB)2.5 160 for adhesive urea resin4,4′-methylenebis(cyclohexyl ((IIIA)100/(IIIB)20) layer (U1)isocyanate)/(IIIB) burette compound of hexamethylene diisocyanateadhesive 4 polyurethane (IIIA) isomer mixture of (IIIA)10/(IIIB)5 150for adhesive urea resin 4,4′-methylenebiscyclohexyl ((IIIA)100/(IIIB)50)layer (U1) isocyanate)/(IIIB) burette compound of hexamethylenediisocyanate adhesive 5 polyurethane (IIIA) isomer mixture of (IIIA)8.5/(IIIB)6.5 140 for adhesive urea resin4,4′-methylenebis(cyclohexyl ((IIIA)100/(IIIB)76) layer (U1)isocyanate)/(IIIB) burette compound of hexamethylene diisocyanateadhesive 6 polyurethane (IIIA) isomer mixture of  (IIIA)7.5/(IIIB)7.5135 for adhesive urea resin 4,4′-methylenebis(cyclohexyl((IIIA)100/(IIIB)20) layer (U1) isocyanate)/(IIIB) burette compound ofhexamethylene diisocyanate adhesive 7 polyurethane (IIIA) isomer mixtureof  (IIIA)6.5/(IIIB)8.5 120 for adhesive urea resin4,4′-methylenebis(cyclohexyl  ((IIIA)100/(IIIB)131) layer (U1)isocyanate)/(IIIB) isocyanurate compound of hexamethylene diisocyanateadhesive 8 polyurethane (IIIA) isomer mixture of (IIIA)10/(IIIB)5 150for adhesive urea resin 4,4′-methylenebis(cyclohexyl((IIIA)100/(IIIB)50) layer (U1) isocyanate)/(IIIB) isocyanurate compoundof hexamethylene diisocyanate *1; This softening point is the softeningpoint of an adhesive layer. *2; amount based on 100 parts by mass of thecomponent (I) Figures within parentheses show the amount of thecomponent (IIIB) based on 100 parts by mass of the component (IIIA).

TABLE 4 Layer configuration of laminate Example 1Polycarbonate/photochromic adhesive layer (photochromic composition1)/polarizing film layer/adhesive layer (adhesive 1 for adhesivelayer)/polycarbonate Example 3 Polycarbonate/photochromic adhesive layer(photochromic composition 1)/polarizing film layer/adhesive layer(acrylic adhesive)/polycarbonate Example 5 Polycarbonate/photochromicadhesive layer (photochromic composition 1)/polarizing filmlayer/adhesive layer (olefin-based adhesive)/polycarbonate Example 7Polycarbonate/photochromic adhesive layer (photochromic composition1)/polarizing film layer/adhesive layer (moisture-curable urethaneadhesive + triisocyanate-based curing agent)/polycarbonate Example 9Polycarbonate/photochromic adhesive layer (photochromic composition1)/polarizing film layer/adhesive layer (polyvinyl alcohol-basedadhesive)/polycarbonate Example 11 Polycarbonate/photochromic adhesivelayer (photochromic composition 1)/ polycarbonate/adhesive layer(adhesive 1 for adhesive layer)/polarizing film layer/adhesive layer(adhesive 1 for adhesive layer)/polycarbonate Example 13Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition 1)/adhesivelayer (adhesive 1 for adhesive layer)/polycarbonate/adhesive layer(adhesive 1 for adhesive layer)/polarizing film layer/adhesive layer(adhesive 1 for adhesive layer)/polycarbonate Example 15Polycarbonate/adhesive layer (moisture-curable urethane adhesive +triisocyanate-based curing agent)/photochromic adhesive layer(photochromic composition 1)/adhesive layer (moisture-curable urethaneadhesive + triisocyanate-based curing agent)/polycarbonate/adhesivelayer (adhesive 1 for adhesive layer)/polarizing film layer/adhesivelayer (adhesive 1 for adhesive layer)/polycarbonate Example 17Polycarbonate/adhesive layer (polyvinyl alcohol-basedadhesive)/photochromic adhesive layer (photochromic composition 1)/adhesive layer (acrylic adhesive)/polycarbonate/adhesive layer (adhesive1 for adhesive layer)/polarizing film layer/adhesive layer (adhesive 1for adhesive layer)/polycarbonate Example 19 Polycarbonate/photochromicadhesive layer (photochromic composition 1)/ TAC/polarizing filmlayer/TAC/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 21 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition 1)/adhesivelayer (adhesive 1 for adhesive layer)/TAC/polarizing filmlayer/TAC/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 23 Polycarbonate/photochromic adhesive layer (photochromiccomposition 2)/ polarizing film layer/adhesive layer (adhesive 1 foradhesive layer)/polycarbonate Example 25 polycarbonate/adhesive layer(adhesive 1 for adhesive layer)/photochromic adhesive layer(photochromic composition 1)/polarizing film layer/adhesive layer(adhesive 2 for adhesive layer)/adhesive layer (adhesive 1 for adhesivelayer)/polycarbonate Example 27 polycarbonate/photochromic adhesivelayer (photochromic composition 3)/polarizing film layer/adhesive layer(adhesive 1 for adhesive layer)/polycarbonate Example 29Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition3)/polarizing film layer/adhesive layer (adhesive 2 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 31 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition1)/polarizing film layer/adhesive layer (adhesive 2 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 33 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition5)/polarizing film layer/adhesive layer (adhesive 3 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 35 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition6)/polarizing film layer/adhesive layer (adhesive 4 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 37 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition7)/polarizing film layer/adhesive layer (adhesive 5 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 39 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition8)/polarizing film layer/adhesive layer (adhesive 6 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 41 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition9)/polarizing film layer/adhesive layer (adhesive 7 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateExample 43 Polycarbonate/adhesive layer (adhesive 1 for adhesivelayer)/photochromic adhesive layer (photochromic composition10)/polarizing film layer/adhesive layer (adhesive 8 for adhesivelayer)/adhesive layer (adhesive 1 for adhesive layer)/polycarbonateComparative Polycarbonate/photochromic adhesive layer (photochromiccomposition Example 1 4)/polarizing film layer/adhesive layer (adhesive1 for adhesive layer)/polycarbonate

TABLE 5 photochromic properties Visual polarization Visual fadingTransmittance degree transmittance speed Durability (%) (%) (%) (sec)(%) Ex. 1 41.0 99.1 11.0 45 93 Ex. 3 41.0 99.1 11.0 45 93 Ex. 5 41.099.1 11.0 45 93 Ex. 7 41.0 99.1 11.0 45 93 Ex. 9 41.0 99.1 11.0 45 93Ex. 11 41.3 99.2 11.0 45 93 Ex. 13 41.5 99.0 11.0 45 93 Ex. 15 41.5 99.011.0 45 93 Ex. 17 41.5 99.0 11.0 45 93 Ex. 19 43.3 99.9 11.0 45 93 Ex.21 43.3 99.9 11.0 45 93 Ex. 23 41.0 99.1 11.0 45 91 Ex. 25 41.0 99.111.0 45 93 Ex. 27 41.0 99.1 11.0 45 93 Ex. 29 41.0 99.1 11.0 45 93 Ex.31 41.0 99.1 11.0 45 93 Ex. 33 41.0 99.1 11.0 45 93 Ex. 35 41.0 99.111.0 45 93 Ex. 37 41.0 99.1 11.0 45 93 Ex. 39 41.0 99.1 11.0 45 93 Ex.41 41.0 99.1 11.0 45 93 Ex. 43 41.0 99.1 11.0 45 93 C. Ex. 1 41.0 99.111.0 45 60 perspiration peel strength(N/25 mm) resistance test roomtemperature 70° C. 150° C. (hours) Ex. 1 150 120 20 400 Ex. 3 120 90 10200 Ex. 5 120 80 10 200 Ex. 7 160 120 20 450 Ex. 9 130 100 15 350 Ex. 11140 110 20 400 Ex. 13 180 125 30 800 Ex. 15 170 125 30 700 Ex. 17 130110 20 500 Ex. 19 140 110 20 400 Ex. 21 180 125 30 800 Ex. 23 140 80 20100 Ex. 25 180 130 40 900 Ex. 27 100 70 10 120 Ex. 29 120 80 10 192 Ex.31 160 125 30 504 Ex. 33 190 130 35 1100 Ex. 35 200 140 35 1300 Ex. 37200 140 35 1300 Ex. 39 180 130 25 1000 Ex. 41 160 100 15 700 Ex. 43 200130 35 1300 C. Ex. 1 80 50 5 24 Ex.: Example C. Ex.: Comparative Example

TABLE 6 photochromic properties Visual polarization Visual fadingTransmittance degree transmittance speed Durability (%) (%) (%) (sec)(%) Ex. 2 40.5 99.1 11.0 45 93 Ex. 4 40.6 99.1 11.0 45 93 Ex. 6 40.699.1 11.0 45 93 Ex. 8 40.6 99.1 11.0 45 93 Ex. 10 40.6 99.1 11.0 45 93Ex. 12 40.6 99.1 11.0 45 93 Ex. 14 40.8 99.0 11.0 45 93 Ex. 16 40.8 99.011.0 45 93 Ex. 18 40.8 99.0 11.0 45 93 Ex. 20 43.2 99.9 11.0 45 93 Ex.22 43.2 99.9 11.0 45 93 Ex. 24 40.5 99.1 11.0 45 91 Ex. 26 40.7 99.111.0 45 93 Ex. 28 40.5 99.1 11.0 45 93 Ex. 30 40.5 99.1 11.0 45 93 Ex.32 40.5 99.1 11.0 45 93 Ex. 34 40.7 99.1 11.0 45 93 Ex. 36 40.7 99.111.0 45 93 Ex. 38 40.7 99.1 11.0 45 93 Ex. 40 40.7 99.1 11.0 45 93 Ex.42 40.7 99.1 11.0 45 93 Ex. 44 40.7 99.1 11.0 45 93 C. Ex. 2 41.0 99.111.0 45 60 perspiration resistance test bending (hours) workability Ex.2 1000 A Ex. 4 500 B Ex. 6 400 B Ex. 8 1000 B Ex. 10 800 B Ex. 12 1000 AEx. 14 1400 A Ex. 16 1300 B Ex. 18 1100 B Ex. 20 900 A Ex. 22 1400 A Ex.24 300 B Ex. 26 1500 A Ex. 28 360 B Ex. 30 480 B Ex. 32 1104 A Ex. 341600 A Ex. 36 1800 A Ex. 38 1800 A Ex. 40 1600 B Ex. 42 1000 A Ex. 441800 A C. Ex. 2 48 C Ex.: Example C. Ex.: Comparative Example

As obvious from the above Examples 1 to 44, it is understood that thelaminate of the present invention in which the polyurethane urea resinis used in the adhesive layer composed of the photochromic compositionhas excellent photochromic properties, polarization properties andexcellent adhesion at a high temperature and in a perspirationresistance test.

As shown in Comparative Examples 1 and 2, when the two-liquid curableurethane resin is used in the adhesive layer composed of thephotochromic composition, photochromic properties (durability) andadhesion are unsatisfactory

Effect of the Invention

The laminate of the present invention exhibits excellent adhesion,polarization properties and photochromic properties. Further, even whenan optical article is manufactured by setting the laminate of thepresent invention in a mold and injection molding a polycarbonate layeras a thermoplastic resin layer in the mold, excellent adhesion isobtained not only for the laminate but also between the laminate and theinjection molded polycarbonate layer, excellent polarization propertiesand photochromic properties are retained, and optical distortion hardlyoccurs.

1. A laminate comprising a pair of polycarbonate optical sheets or filmswhich are laminated together through a polarizing film layer and anadhesive layer of a photochromic composition comprising (I) apolyurethane urea resin and (II) a photochromic compound.
 2. Thelaminate according to claim 1, wherein the weight average molecularweight/number average molecular weight ratio indicative ofpolydispersity of the polyurethane urea resin (I) is 1.6 to 2.4.
 3. Thelaminate according to claim 1, wherein the photochromic compositionfurther comprises (III) a polyisocyanate compound having at least twoisocyanate groups in the molecule.
 4. The laminate according to claim 3,wherein the polyisocyanate compound having at least two isocyanategroups in the molecule (III) is at least one polyisocyanate compoundselected from the group consisting of a compound having an isocyanategroup bonded to a secondary carbon, hexamethylene diisocyanate, burettecompound of hexamethylene diisocyanate, isocyanurate compound ofhexamethylene diisocyanate and adduct compound of hexamethylenediisocyanate.
 5. The laminate according to claim 4, wherein thepolyisocyanate compound having at least two isocyanate groups in themolecule (III) comprises (IIIA) a compound having an isocyanate groupbonded to a secondary carbon and (IIIB) at least one compound selectedfrom the group consisting of hexamethylene diisocyanate, burettecompound of hexamethylene diisocyanate, isocyanurate compound ofhexamethylene diisocyanate and adduct compound of hexamethylenediisocyanate.
 6. The laminate according to claim 5, wherein thepolyisocyanate compound having at least two isocyanate groups in themolecule (III) comprises 100 parts by mass of the compound having anisocyanate group bonded to a secondary carbon (IIIA) and 20 to 150 partsby mass of at least one compound (IIIB) selected from the groupconsisting of hexamethylene diisocyanate, burette compound ofhexamethylene diisocyanate, isocyanurate compound of hexamethylenediisocyanate and adduct compound of hexamethylene diisocyanate.
 7. Thelaminate according to claim 1, wherein the polyurethane urea resin (I)is a reaction product of (A) a urethane prepolymer having an isocyanategroup at the end of the molecule, (B) a polyamine compound having atleast two amino groups in the molecule and (C) a compound having onegroup able to react with an isocyanate group in the molecule.
 8. Thelaminate according to claim 1, wherein the polycarbonate optical sheetor film and the polarizing film layer and/or the polarizing film layerand the adhesive layer of the photochromic composition are laminatedtogether through an adhesive layer containing no photochromic compound.9. The laminate according to claim 1, wherein at least one optical sheetor film is existent between the polarizing film layer and the adhesivelayer of the photochromic composition.
 10. The laminate according toclaim 1, wherein a cellulose triacetate film is laminated on both sidesof the polarizing film layer.
 11. The laminate according to claim 1,wherein the softening point of the adhesive layer of the photochromiccomposition is not lower than 100° C.
 12. The laminate according claim8, wherein the softening points of the adhesive layer of thephotochromic composition and the adhesive layer containing nophotochromic compound are not lower than 100° C.
 13. The laminateaccording to claim 8, wherein the polycarbonate optical sheet or film,the adhesive layer containing no photochromic compound, the adhesivelayer of the photochromic composition, the polarizing film layer, theadhesive layer containing no photochromic compound and the polycarbonateoptical sheet or film are laminated in this order.
 14. The laminateaccording to claim 13, wherein the adhesive layer of the photochromiccomposition described before the polarizing film differs from theadhesive layer containing no photochromic compound described after thepolarizing film only in that the former layer contains the photochromiccompound.
 15. The laminate according to claim 13, wherein an adhesivelayer which differs from the adhesive layer containing no photochromiccompound is further existent between the adhesive layer containing nophotochromic compound described after the polarizing film layer and thepolycarbonate optical sheet or film.
 16. An optical article manufacturedby laminating a polycarbonate layer on the front surface of apolycarbonate optical sheet or film on the polarizing film layer side ofthe laminate of claim 1.